US4091157A
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Heat-curable composite adhesive sheet and method for making
Assignee: Nitto Denko Corp
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Filing: 1976-02-04
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Granted: 1978-05-23
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Expires: 1996-02-04
Abstract
Abstract A heat-curable multilayer composite sheet comprising a layer comprising one or more unsaturated compounds which are normally solid or liquid free radical reactive unsaturated compounds and a layer comprising a normally solid or liquid free radical initiator, the layers being bonded to each other as a laminate as separate layers at a temperature at which the free radical initiator does not lose its free radical reaction initiating capability, and, A process for preparing a heat-curable multilayer composite sheet, which comprises coating a layer-forming material containing a normally solid or liquid free radical reactive unsaturated compound on a strippable sheet to form an unsaturated compound material layer on the strippable sheet, coating a layer-forming material containing a normally solid or liquid free radical initiator on a strippable sheet to form a free initiator layer on the strippable sheet, bringing the unsaturated compound material layer into contact with the free radical initiator layer, and bonding them to each other at a temperature at which the free radical initiator layer does not lose its free radical reaction initiating ability.
Inventors
- 👤 Yutaka Hori
- 👤 Hidekazu Takahashi
- 👤 Makoto Sunakawa
- 👤 Ichiro Ijichi
- 👤 Kiyohiro Kamei
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 15:50
CPC Classifications
C; C09; C09J; C09J7/00; C09J7/10; B; B32; B32B; B32B27/00; B32B27/06; B32B27/065; B32B27/12; B32B27/30; B32B27/308; B32B5/00; B32B5/02; B32B5/022; B32B5/18; B32B7/00; B32B7/04; B32B7/06; B32B7/10; B32B7/12; B32B2260/00; B32B2260/02; B32B2260/021; B32B2260/04; B32B2260/046; B32B2451/00; C09J2301/00; C09J2301/10; C09J2301/12; C09J2301/124; C09J2301/1242; C09J2301/20; C09J2301/208; Y; Y10; Y10T; Y10T428/00; Y10T428/14; Y10T428/1452; Y10T428/24; Y10T428/24802; Y10T428/2481; Y10T428/24851; Y10T428/2486; Y10T428/24942; Y10T428/2495; Y10T428/24967; Y10T428/249921; Y10T428/249953; Y10T428/249987; Y10T428/249991; Y10T428/249992; Y10T428/26; Y10T428/266; Y10T428/28; Y10T428/2813; Y10T428/2817; Y10T428/2826; Y10T428/2839; Y10T428/2848; Y10T428/2852; Y10T428/2878; Y10T428/2887; Y10T428/2891; Y10T428/29; Y10T428/2913; Y10T428/298; Y10T428/31504; Y10T428/31511; Y10T428/31515; Y10T428/31536; Y10T428/31551; Y10T428/31645; Y10T428/31649; Y10T428/31855; Y10T428/3188; Y10T428/31895; Y10T428/31909; Y10T428/31928; Y10T442/00; Y10T442/60; Y10T442/674; Y10T442/676
Claims Analysis
Total Claims: 67
Claim 1
Independent Claim
159 words
A heat-curable composite sheet comprising a first layer comprising at least one unsaturated compound which is free radical reactive selected from the group consisting of i. an unsaturated polymer containing at least two double bonds per molecule; ii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated monomer; or iii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated polymer containing one double bond per molecule, and a second layer comprising a solid or liquid free radical initiator, said layers being bonded to each other in a laminate as separate layers at a temperature at which the free radical initiator does not lose its free radical initiating capability, wherein said sheet is capable of being cured by the melting and mixing together of the first and second layers at a temperature at which a free radical reaction takes place in said composite sheet.
Claim 2
Dependent Claim
159 words
A heat-curable composite sheet comprising a first layer comprising at least one unsaturated compound which is free radical reactive selected from the group consisting of i. an unsaturated polymer containing at least two double bonds per molecule; ii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated monomer; or iii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated polymer containing one double bond per molecule, and a second layer comprising a solid or liquid free radical initiator, said layers being bonded to each other in a laminate as separate layers at a temperature at which the free radical initiator does not lose its free radical initiating capability, wherein said sheet is capable of being cured by the melting and mixing together of the first and second layers at a temperature at which a free radical reaction takes place in said composite sheet.
Claim 3
Dependent Claim
63 words
The composite sheet of claim 1, wherein the unsaturated compound is said mixture (iii) and the amount of double bonds in the unsaturated compound is about 10 19 to about 10 21 per gram, and the proportion of the double bonds in the polymer containing at least two double bonds per molecule is at least 0.1% based on the total double bond content.
Claim 4
Dependent Claim
35 words
The composite sheet of claim 2, wherein the proportion of double bonds in the polymer containing at least two double bonds per molecule is at least about 1.0% based on the total double bond content.
Claim 5
Dependent Claim
38 words
The composite sheet of claim 2, wherein the proportion of double bonds in the polymer containing at least two double bonds per molecule is at least 10% but less than 100% based on the total double bond content.
Claim 6
Dependent Claim
68 words
The composite sheet of claim 1, wherein the unsaturated polymer containing at least two double bonds per molecule is an acrylic unsaturated polymer of the formula: ##STR2## wherein X is a hydrogen atom or a methyl group, and Y is a residue of a member selected from the group consisting of polyesters, polyurethanes, epoxy compounds and polyglycols, which has a molecular weight of not more than about 5,000.
Claim 7
Dependent Claim
31 words
The composite sheet of claim 5, wherein the unsaturated compound comprises the acrylic unsaturated polymer and about 0.1 to about 100% by weight, based on he polymer, of an unsaturated monomer.
Claim 8
Dependent Claim
46 words
The composite sheet of claim 1, wherein the amount of the initiator, in terms of the number of active free radicals generated from the initiator, is about 0.1 to about 1,000 per 1,000 double bonds of the unsaturated compound per unit area of the composite sheet.
Claim 9
Dependent Claim
44 words
The composite sheet of claim 1, wherein the amount of the initiator, in terms of the number of active free radicals generated from the initiator, is 1 to 100 per 1,000 double bonds of the unsaturated compound per unit area of the composite sheet.
Claim 10
Dependent Claim
44 words
The composite sheet of claim 1, wherein the amount of the initiator, in terms of the number of active free radicals generated from the initiator, is 5 to 50 per 1,000 double bonds of the unsaturated compound per unit area of the composite sheet.
Claim 11
Dependent Claim
15 words
The composite sheet of claim 1, wherein the first layer further comprises a non-reactive carrier.
Claim 12
Dependent Claim
25 words
The composite sheet of claim 10, wherein the amount of the non-reactive carrier is not more than about 500% by weight of the unsaturated compound.
Claim 13
Dependent Claim
24 words
The composite sheet of claim 10, wherein the amount of the non-reactive carrier is not more than 200% by weight of the unsaturated compound.
Claim 14
Dependent Claim
25 words
The composite sheet of claim 10, wherein the amount of the non-reactive carrier is not more than 100% by weight based on the unsaturated compound.
Claim 15
Dependent Claim
14 words
The composite sheet of claim 10, wherein the non-reactive carrier is a hot-melt adhesive.
Claim 16
Dependent Claim
15 words
The composite sheet of claim 1, wherein the second layer further comprises a non-reactive carrier.
Claim 17
Dependent Claim
25 words
The composite sheet of claim 15, wherein the amount of the non-reactive carrier is not more than about 2,000% by weight based on the initiator.
Claim 18
Dependent Claim
24 words
The composite sheet of claim 15, wherein the amount of the non-reactive carrier is not more than 1,000% by weight based on the initiator.
Claim 19
Dependent Claim
24 words
The composite sheet of claim 15, wherein the amount of the non-reactive carrier is not more than 100% by weight based on the initiator.
Claim 20
Dependent Claim
22 words
The composite sheet of claim 1, wherein the second layer is supported by a fibrous base material or a plastic foam sheet.
Claim 21
Dependent Claim
15 words
The composite sheet of claim 19, wherein the fibrous base material is a non-woven fabric.
Claim 22
Dependent Claim
51 words
The composite sheet of claim 19, wherein the fibrous base material is a non-woven fabric of organic fibers having a denier size of about 1 to about 12 denier, a specific volume of about 1 to about 10 cm 3 /g, and a thickness of about 0.02 to about 1.0 mm.
Claim 23
Dependent Claim
36 words
The composite sheet of claim 21, wherein the fibrous material has a denier size of 3 to 5, a specific volume of 2 to 5 m 3 /g and a thickness of 0.04 to 0.05 mm.
Claim 24
Dependent Claim
27 words
The composite sheet of claim 20, wherein the amount of the initiator applied to the fibrous base material is about 0.5 to about 100 g/m 2 .
Claim 25
Dependent Claim
22 words
The composite sheet of claim 1, wherein the first layer is supported by a fibrous base material or a plastic foam sheet.
Claim 26
Dependent Claim
17 words
The composite sheet of claim 19, wherein the fibrous base material or plastic foam sheet is colored.
Claim 27
Dependent Claim
21 words
The composite sheet of claim 19, wherein the fibrous base material or plastic foam sheet has a color design printed thereon.
Claim 28
Dependent Claim
13 words
The composite sheet of claim 19, wherein the fibrous base material is heat-shrinkable.
Claim 29
Dependent Claim
23 words
The composite sheet of claim 1, wherein the initiator is a peroxide radical initiator, an azo radical initiator or an inorganic radical initiator.
Claim 30
Dependent Claim
30 words
The composite sheet of claim 28, wherein the initiator is a peroxide radical initiator and is selected from the group consisting of a peroxide, a peracid or a peroxy ester.
Claim 31
Dependent Claim
12 words
The composite sheet of claim 1, wherein the initiator is benzoyl peroxide.
Claim 32
Dependent Claim
21 words
The composite sheet of claim 1, wherein the first layer is bonded and laminated to both surfaces of the second layer.
Claim 33
Dependent Claim
26 words
The composite sheet of claim 1, wherein the unsaturated compound layer and the initiator layer both have a thickness of about 0.01 to about 1.0 mm.
Claim 34
Dependent Claim
41 words
The composite sheet of claim 5, which comprises: a substrate comprising a non-woven sheet of organic fibers impregnated with benzoyl peroxide and a non-reactive carrier having on both faces thereof a layer comprising said acrylic unsaturated polymer and a non-reactive carrier.
Claim 35
Dependent Claim
41 words
The composite sheet of claim 1, wherein said melting and mixing together is accomplished by heating at a temperature of about 70 to about 120° C and pressing at a pressure of about 10g/cm 2 to about 10 kg/cm 2 .
Claim 36
Dependent Claim
41 words
The composite sheet of claim 1, wherein no curing of said sheet occurs at room temperature and said sheet storable for more than six months at a temperature of not more than 50° C with the retention of its curing capability.
Claim 37
Dependent Claim
109 words
The composite sheet of claim 1, wherein said unsaturated polymer containing at least two double bonds per molecule is selected from the group consisting of a. an acryclic unsaturated polymer of the formula ##STR3## wherein X is a hydrogen atom or a methyl group, and Y is a residue of a member selected from the group consisting of polyesters, polyurethanes, epoxy compounds and polyglycols, which has a molecular weight of not more than about 5,000; b. an unsaturated polyester resin having a molecular weight of about 1,000 to about 50,000; or c. an unsaturated polymer precursor having a molecular having a molecular weight of about 100 to about 5000.
Claim 38
Dependent Claim
60 words
The composite sheet of claim 1, wherein said unsaturated monomer in mixture (ii) is selected from the group consisting of triallyl cyanurate, tolylene diallyl carbamate diallyl isocyanurate; N-methylol acrylamide, acrylamide, methylacrylamide, N-tertiary butyl acrylamide, diacetone acrylamide, triacryl formal, ethyl acrylate, butyl acrylate, vinyl stearate, N-vinyl carbazole, divinylbenzene, divinyl ethylene glycol, maleimide, dimethyl itaconate, acenaphthylene, diallyl phthlate or trimethylol propane trimethacrylate.
Claim 39
Dependent Claim
15 words
The composite sheet of claim 36, wherein said polymer precursor is a diallyl phthalate prepolymer.
Claim 40
Dependent Claim
34 words
The composite sheet of claim 1, wherein said unsaturated compound is mixture (ii) and the amount of unsaturated monomer in the mixture is about 0.1 to about 100% by weight based on the polymer.
Claim 41
Dependent Claim
17 words
The composite sheet of claim 39, wherein said amount is about 1 to about 30% by weight.
Claim 42
Dependent Claim
83 words
The composite sheet of claim 36, wherein said unsaturated polyester resin (b) is synthesized by esterifying an acid component composed of at least one unsaturated carboxylic acid and a saturated polybasic carboxylic acid with a polyhydric alcohol and wherein said unsaturated polymer precursor (c) is synthesized by polymerizing, to an about 2 to about 50 degrees of polymerization, one or more monomers having two or more double bonds per molecule in which at least one double bond per molecule remains in the precursor.
Claim 43
Dependent Claim
17 words
The composite sheet of claim 10, wherein said non-reactive carrier is a thermoplastic resin or a rubber.
Claim 44
Dependent Claim
159 words
A process for producing a heat-curable multilayer composite sheet, which comprises heat softening a first layer comprising at least one unsaturated compound which is free radical reactive selected from the group consisting of i. an unsaturated polymer containing at least two double bonds per molecule; ii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated monomer; or iii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated polymer containing one double bond per molecule, and a second layer comprising a solid or liquid free radical initiator at a temperature at which the free radical initiator does not lose its free radical reaction initiating ability, to thereby render said first layer tacky followed by bonding the first and second layers to each other, wherein said composite sheet is capable of being cured by the melting and mixing together of the first and second layers.
Claim 45
Dependent Claim
159 words
A process for producing a heat-curable multilayer composite sheet, which comprises heat softening a first layer comprising at least one unsaturated compound which is free radical reactive selected from the group consisting of i. an unsaturated polymer containing at least two double bonds per molecule; ii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated monomer; or iii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated polymer containing one double bond per molecule, and a second layer comprising a solid or liquid free radical initiator at a temperature at which the free radical initiator does not lose its free radical reaction initiating ability, to thereby render said first layer tacky followed by bonding the first and second layers to each other, wherein said composite sheet is capable of being cured by the melting and mixing together of the first and second layers.
Claim 46
Dependent Claim
32 words
The process of claim 43, wherein said temperature at which the free radical initiator layer does not lose its free radical reaction initiating ability is from about 40° to about 70° C.
Claim 47
Dependent Claim
108 words
The process of claim 43, wherein said unsaturated polymer containing at least two double bonds per molecule is selected from the group consisting of a. an acryclic unsaturated polymer of the formula ##STR4## wherein X is a hydrogen atom or a methyl group, and Y is a residue of a member selected from the group consisting of polyesters, polyurethanes, epoxy compounds and polyglycols, which has a molecular weight of not more than about 5,000; b. an unsaturated polyester resin having a molecular weight of about 1,000 to about 50,000; or c. an unsaturated polymer precursor having a molecular having a molecular weight of about 100 to about 5000.
Claim 48
Dependent Claim
59 words
The process of claim 43, wherein said unsaturated monomer in mixture (ii) is selected from the group consisting of triallyl cyanurate; tolylene diallyl carbamate diallyl isocyanurate, N-methylol acrylamide, acrylamide, methylacrylamide, N-tertiary butyl acrylamide, diacetone acrylamide, triacryl formal, ethyl acrylate, butyl acrylate, vinyl stearate, N-vinyl carbazole, divinylbenzene, divinyl ethylene glycol, maleimide, dimethyl itaconate, acenaphthylene, diallyl phthalate or trimethylol propane trimethacrylate.
Claim 49
Dependent Claim
14 words
The process of claim 45, wherein said polymer precursor is a diallyl phthalate prepolymer.
Claim 50
Dependent Claim
62 words
The process of claim 37, wherein the unsaturated compound is said mixture (iii) and the amount of double bonds in the unsaturated compound is about 10 19 to about 10 21 per gram, and the proportion of the double bonds in the polymer containing at least two double bonds per molecule is at least 0.1% based on the total double bond content.
Claim 51
Dependent Claim
34 words
The process of claim 48, wherein the proportion of double bonds in the polymer containing at least two double bonds per molecule is at least about 1.0% based on the total double bond content.
Claim 52
Dependent Claim
37 words
The process of claim 48, wherein the proportion of double bonds in the polymer containing at least two double bonds per molecule is at least 10% but less than 100% based on the total double bond content.
Claim 53
Dependent Claim
33 words
The process of claim 43, wherein said unsaturated compound is mixture (ii) and the amount of unsaturated monomer in the mixture is about 0.1 to about 100% by weight based on the polymer.
Claim 54
Dependent Claim
16 words
The process of claim 51, wherein said amount is about 1 to about 30% by weight.
Claim 55
Dependent Claim
81 words
The process of claim 43, wherein said unsaturated polyester resin (b) is synthesized by esterifying an acid component composed of at least one unsaturated carboxylic acid and a saturated polybasic carboxylic acid with a polyhydric alcohol and wherein said unsaturated polymer precursor (c) is synthesized by polymerizing, to an about 2 to about 50° of polymerization, one or more monomers having two or more double bonds per molecule in which at least one double bond per molecule remains in the precursor.
Claim 56
Dependent Claim
136 words
A process for producing a heat-curable multilayer sheet which comprises bonding, without heating and at a room temperature of about 15° to about 25° C, a tacky first layer comprising at least one unsaturated compound which is free radical reactive selected from the group consisting of i. an unsaturated polymer containing at least two double bonds per molecule; ii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated monomer; or iii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated polymer containing one double bond per molecule, to a second layer comprising a solid or liquid free radical initiator, wherein said composite sheet is capable of being cured by the melting and mixing together of the first and second layers.
Claim 57
Dependent Claim
136 words
A process for producing a heat-curable multilayer sheet which comprises bonding, without heating and at a room temperature of about 15° to about 25° C, a tacky first layer comprising at least one unsaturated compound which is free radical reactive selected from the group consisting of i. an unsaturated polymer containing at least two double bonds per molecule; ii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated monomer; or iii. a mixture of an unsaturated polymer containing at least two double bonds per molecule and an unsaturated polymer containing one double bond per molecule, to a second layer comprising a solid or liquid free radical initiator, wherein said composite sheet is capable of being cured by the melting and mixing together of the first and second layers.
Claim 58
Dependent Claim
33 words
The process of claim 54, wherein said bonding is accomplished by passing said first and second layers between two rolls having a roll pressure of about 0.5 to about 10 kg/cm 2 .
Claim 59
Dependent Claim
108 words
The process of claim 54, wherein said unsaturated polymer containing at least two double bonds per molecule is selected from the group consisting of a. an acryclic unsaturated polymer of the formula ##STR5## wherein X is a hydrogen atom or a methyl group, and Y is a residue of a member selected from the group consisting of polyesters, polyurethanes, epoxy compounds and polyglycols, which has a molecular weight of not more than about 5,000; b. an unsaturated polyester resin having a molecular weight of about 1,000 to about 50,000; or c. an unsaturated polymer precursor having a molecular having a molecular weight of about 100 to about 5000.
Claim 60
Dependent Claim
59 words
The process of claim 54, wherein said unsaturated monomer in mixture (ii) is selected from the group consisting of triallyl cyanurate, tolylene diallyl carbamate diallyl isocyanurate; N-methylol acrylamide, acrylamide, methylacrylamide, N-tertiary butyl acrylamide, diacetone acrylamide, triacryl formal, ethyl acrylate, butyl acrylate, vinyl stearate, N-vinyl carbazole, divinylbenzene, divinyl ethylene glycol, maleimide, dimethyl itaconate, acenaphthylene, diallyl phthalate or trimethylol propane trimethacrylate.
Claim 61
Dependent Claim
14 words
The process of claim 56, wherein said polymer precursor is a diallyl phthalate prepolymer.
Claim 62
Dependent Claim
62 words
The process of claim 54 wherein the unsaturated compound is said mixture (iii) and the amount of double bonds in the unsaturated compound is about 10 19 to about 10 21 per gram, and the proportion of the double bonds in the polymer containing at least two double bonds per molecule is at least 0.1% based on the total double bond content.
Claim 63
Dependent Claim
34 words
The process of claim 59 wherein the proportion of double bonds in the polymer containing at least two double bonds per molecule is at least about 1.0% based on the total double bond content.
Claim 64
Dependent Claim
37 words
The process of claim 59 wherein the proportion of double bonds in the polymer containing at least two double bonds per molecule is at least 10% but less than 100% based on the total double bond content.
Claim 65
Dependent Claim
33 words
The process of claim 54, wherein said unsaturated compound is mixture (ii) and the amount of unsaturated monomer in the mixture is about 0.1 to about 100% by weight based on the polymer.
Claim 66
Dependent Claim
16 words
The process of claim 62, wherein said amount is about 1 to about 30% by weight.
Claim 67
Dependent Claim
81 words
The process of claim 54, wherein said unsaturated polyester resin (b) is synthesized by esterifying an acid component composed of at least one unsaturated carboxylic acid and a saturated polybasic carboxylic acid with a polyhydric alcohol and wherein said unsaturated polymer precursor (c) is synthesized by polymerizing, to an about 2 to about 50° of polymerization, one or more monomers having two or more double bonds per molecule in which at least one double bond per molecule remains in the precursor.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-05-22 | 1981-11-21 | 1982-05-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-05-22 | 1985-11-21 | 1986-05-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-05-22 | 1989-11-21 | 1990-05-23 | $7700.00 | Window Closed / Lapsed |