JPH0475943B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention is applicable to plastic films, metal foils, paper,
This invention relates to an adhesive composition that has excellent peel strength against various adherends such as cloth, and has good flexibility and durability. <Conventional technology> Conventionally, various types of adhesives, such as organic solvent-based adhesives, water-based adhesives, and solvent-free adhesives, have been used depending on the material of the adherend and its purpose. ing. Adhesives containing solvents, such as organic solvent-based and water-based adhesives, can be used on adherends where the solvent can be removed by penetration or volatilization, such as paper or cloth; It cannot be used for adherends that are impermeable to solvents or cannot be volatilized. Therefore, for these combinations of adherends that are impermeable to solvents, heat seal bonding is performed after the solvent has been volatilized, or a solvent-free adhesive is used. For example, it is known that a linear saturated polyester resin can be dissolved in a solvent and used as an adhesive for adhesives such as polyester film and aluminum foil, which have relatively poor adhesive properties.
52−15092). This product is bonded by applying an adhesive to the adherend, evaporating the solvent, and then heat-sealing it. Polyester film/polyester film, aluminum foil/ The peel strength of aluminum foil is only 603 g/cm and 615 g/cm at maximum, respectively, and it cannot be said that it has sufficient adhesive performance. Similarly, adhesives made by dissolving chloroprene rubber in a solvent are also used to bond polyester films, aluminum foils, etc., but generally these polyester films, aluminum foils, etc. and solvents such as cloth and paper are volatilized. It is used in combination with adherends that
polyester film/polyester film,
Not used in combinations such as aluminum foil/aluminum foil. On the other hand, solvent-free adhesives include two-component reactive epoxy adhesives, cyanoacrylate adhesives,
Hot melt adhesives, reactive acrylic adhesives, and the like are known. Among these adhesives, reactive acrylic adhesives react at room temperature by using organic peroxides and reducing agents as curing agents, and exhibit strength that can be handled within minutes to tens of minutes. The protruding parts that come into contact with the air also harden, and its adhesive properties are excellent in shear, impact, and peel strength, so it has been showing rapid growth in recent years. These reactive acrylic adhesives are
A methacrylic acid alkyl ester and 2-hydroxyalkyl methacrylate as shown in 28178 are used in combination, and a butadiene-based elastomer,
Acrylic adhesives are cured by contacting or mixing a solution containing hydroperoxide, etc. with the reducing component of a redox catalyst, or acrylic monomers and tris(dimethylaminomethyl)phenol as shown in Japanese Patent Publication No. 56-9954. polyester resin to adjust workability such as content and viscosity;
Acrylic adhesives are known that are cured by bringing a solution containing a reducing agent or the like into contact with an accelerator containing hydroperoxide. However, the purpose of these reactive adhesives is mainly for adhesion of metals, and at the same time they have strong adhesion to metals and have the property that their cured products are hard. Therefore, the plastic film that is the object of the present invention,
When bonding highly flexible adherends such as metal foil, cloth, paper, etc. and bending the adhesive, the adhesive layer is hard and will break, which is a big problem in practical terms. becomes. Moreover, when these adhesives are used to bond polyester film, aluminum foil, etc. and the peel strength is measured, the cohesive force of the adhesive layer is strong and the adhesion to the adherend is weak. This has disadvantages such as interfacial peeling from the adhesive and failure to obtain sufficient adhesive strength. As mentioned above, conventionally known adhesives are capable of bonding various adherends with a single type of adhesive, and have good workability and exhibit strength within a few minutes to several tens of minutes at room temperature. The reality is that there are no drugs available. <Problems to be Solved by the Invention> The adhesive composition of the present invention has the following properties:
It improves the shortcomings of conventional adhesives. (1) With conventional adhesives, it was difficult to bond adherends made of different materials such as plastic film, metal foil, paper, and cloth with a single type of adhesive, but the adhesive composition of the present invention It is possible to bond these various adherends with one type of adhesive, and it is especially effective for polyester film and aluminum foil, for which conventional adhesives did not have sufficient peel strength. This indicates peel strength. (2) Conventional reactive acrylic adhesives have a hardened adhesive layer that is extremely hard because their main purpose is to bond metals, but the adhesive composition of the present invention is extremely flexible. It gives a cured product rich in (3) Conventionally, plastic film, metal foil, paper,
Rubber-based solvent-based adhesives are used when bonding various adherends such as cloth with a single type of adhesive, but rubber-based adhesives have high heat deterioration resistance,
Although it had a drawback of poor durability such as moisture resistance, the adhesive composition of the present invention has extremely excellent durability. (4) Among conventionally known adhesives, rubber adhesives can bond various adherends with one type of adhesive, but it takes several hours to several tens of hours to bond. There was a problem with work speed. The adhesive composition of the present invention solves all of these drawbacks, allows various adherends to be bonded with a single type of adhesive, and is highly workable, allowing bonding in a few minutes to several tens of minutes at room temperature. It is a good adhesive. <Means for Solving the Problems> As a result of intensive studies to improve the above-mentioned problems, the inventors of the present invention have found that conventional rubber-based solvent-based adhesives or reactive acrylic adhesives cannot be used. The present inventors have discovered an adhesive composition that exhibits excellent adhesive performance and workability, and have completed the present invention. That is, the present invention includes (A) 20 to 94% by weight of a polymerizable substance having at least one unsaturated double bond in the molecule, and having the general formula CH ₂ =CR ₁ -CO(- OCH ₂ CHR ₂ −)
nOR ₃ (However, R ₁ and R ₂ are hydrogen or methyl groups,
R ₃ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a carbon number 1
a phenyl group having ~4 alkyl substituents,
n represents an integer from 2 to 27. (hereinafter, this polymerizable substance is abbreviated as GA monomer) 5 to 70% by weight, (B) a polyester resin soluble in the polymerizable substance 5
~60% by weight, (C) 0.1 to 20% by weight of an organic peroxide, and (D) 0.05 to 15% by weight of a reducing agent capable of generating radicals upon contact with the organic peroxide. This is an adhesive composition. This adhesive composition is quick-curing, can bond various adherends such as plastic film, metal foil, paper, and cloth with one type of adhesive, and has excellent peel strength.
Moreover, it has good flexibility and durability. The most distinctive feature of the composition of the present invention is that it uses a GA monomer represented by the above general formula as a polymerizable substance and a soluble polyester resin. It forms an extremely flexible cured product that was unimaginable with acrylic adhesives, and also has excellent peel strength and durability on various adherends such as plastic film, metal foil, paper, and cloth. In particular, it exhibits exceptional adhesion to polyester film, aluminum foil, etc., which have traditionally been difficult to adhere to. Furthermore, it is possible to bond combinations of adherends that would be difficult to achieve with conventional rubber adhesives, and the workability is very good as it can be cured in a few minutes to several tens of minutes at room temperature. As mentioned above, the present invention is an acrylic adhesive composition containing GA monomer as a polymerization component, but it is also possible to use only GA monomer as the polymerizable substance, but it is possible to improve the adhesive composition that remains on the surface when the composition is cured. In order to achieve this, it is preferable to include polymerizable substances such as other monomers and oligomers. In addition, in the above general formula, when n is relatively large, the GA monomer is solid at room temperature, but when other polymerizable substances are used together, the GA monomer dissolves in the polymerizable substance, and the polyester resin also dissolves. As it dissolves, a preferred adhesive composition is obtained. An embodiment of the adhesive composition of the present invention is as follows: (A) 20 to 94% by weight, preferably 20 to 94% by weight of a polymerizable substance having at least one unsaturated double bond in the molecule;
Contains 40 to 80% by weight, among all polymerizable substances, general formula CH ₂ = CR ₁ −CO (−OCH ₂ CHR ₂ −)
nOR ₃ (However, R ₁ and R ₂ are hydrogen or methyl groups,
R ₃ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a carbon number 1
a phenyl group having ~4 alkyl substituents,
(n represents an integer of 2 to 27) 5 to 70% by weight, preferably 10 to 60% by weight of a GA monomer; (B) 5 to 60% by weight of a polyester resin soluble in the polymerizable monomer, preferably (C) organic peroxide 0.1-20% by weight, preferably 1.0
~10% by weight, (D) 0.05~15% by weight of a reducing agent capable of generating radicals upon contact with the organic peroxide, preferably
Contains 0.1 to 10% by weight of A, B, C, and D4 components, and cures in a few minutes to tens of minutes at room temperature by contacting an organic peroxide with a reducing agent, and is faster than conventional acrylic reactions. It creates a cured product with flexibility that would have been unimaginable using mold adhesive technology, and also exhibits excellent peel strength against plastic film, metal foil, paper, cloth, etc. In this embodiment, component A contains 20 to 94% by weight, preferably 40 to 80% by weight of a polymerizable substance having at least one unsaturated double bond in the molecule.
Contains 5 to 70 GA monomers in this polymerizable material.
% by weight, preferably 10-60% by weight. When the content of the GA monomer exceeds 70% by weight, the cured product produced by the reaction becomes too sticky and soft, and conversely the adhesive strength becomes weak. 5% by weight
If the amount is less, the adhesion to plastic film and metal foil will be weak. When R ₃ in the GA monomer is an alkyl group or a phenyl group having an alkyl substituent, the number of carbon atoms in the alkyl group is 1 to 4, and when it is 5 or more, the cured product becomes soft and sufficient adhesive strength cannot be obtained. do not have. Further, n is in the range of 2 to 27, and if it exceeds this value, the adhesion will deteriorate and at the same time the viscosity of the final formulation will increase, resulting in poor workability. The number of n does not need to be a certain pure product;
The object of the present invention can be achieved if monomers having different numbers of the above structures are mixed and the average number n is 27 or less. The GA monomer having the above structure is as follows:
For example, methoxydiethylene glycol (meth)
acrylate, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate up to n=27,
The following examples include polyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, etc. in which the number n is within the above range. These GA monomers may be used alone or in combination with other polymerizable substances.
If the ratio of monomers used is within the above range, the object of the present invention can be achieved. Examples of polymerizable substances other than the GA monomer that can be used include monomers or oligomers, such as alkyl esters of acrylic acid or methacrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and dimethyl. Acrylic monomers such as aminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, glycidyl methacrylate, oligomers such as urethane acrylate, epoxy acrylate, and polyester acrylate. can give. These monomers or oligomers can be used in combinations that do not impede the purpose of the present invention within the range of the ratio of the remaining amount after subtracting the GA monomer from the polymerizable material. The polyester resin used in the present invention is a soluble polyester resin obtained by the reaction of dibasic acid and glycol, and dibasic acids include terephthalic acid, isophthalic acid, orthophthalic acid, adipic acid, sebacic acid, and naphthalene dicarboxylic acid. , diphenyldicarboxylic acid, hexahydrophthalic acid, p-oxybenzoic acid, etc.
Glycol components include ethylene glycol,
propylene glycol, diethylene glycol,
Examples include neopencel glycol, tetramethylene glycol, triethylene glycol, cyclohexanediol, xylylene glycol, bisphenol A, and the like. Those obtained by appropriately combining these components and having a molecular weight of 5,000 to 25,000 can be used. By using such a polyester resin as an elastomer component, adhesion to plastic films and metal foils is improved, and furthermore, since an appropriate viscosity is imparted to the adhesive composition, good workability can be obtained. The proportion of polyester resin used in the adhesive composition is 5 to 60% by weight, preferably 10 to 50% by weight. If the proportion of polyester resin used is less than 5% by weight, the adhesion to plastic films and metal foils will decrease and the viscosity of the adhesive composition will become too low, making it impossible to maintain good workability. If the usage ratio exceeds 60% by weight, the solubility in polymerizable substances such as monomers will deteriorate, and the viscosity of the adhesive composition will increase, resulting in poor workability, which is not preferable. Several types of polyester resins can be used in combination depending on the purpose. Organic peroxides used in the present invention include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tertiary butyl peroxide, pinene hydroperoxide, paramenthane hydroperoxide, diisopropyl hydroperoxide, and cumene hydroperoxide. oxide, diisopropylbenzene dihydroperoxide,
Examples include, but are not limited to, tertiary butyl hydroperoxide. The amount of organic peroxide used is 0.1 in the adhesive composition.
~20% by weight, preferably 1.0-10% by weight,
If it is less than 0.1% by weight, the curing speed will be slow, and if it is less than 20% by weight.
In the above case, the adhesion to plastic film and metal foil deteriorates, which is not preferable. The usage of organic peroxide in the present invention is, for example, as follows. (b) Pre-applying an organic peroxide as it is, or dissolving it in a solvent such as acetone, ethyl acetate, or 1,1,1-trichloroethane, or dispersing it in a plasticizer such as dioctyl phthalate or dibutyl phthalate. How to use it: apply it to the body, then apply the following composition containing a reducing agent and cure by reaction. (b) A composition containing a polymerizable substance and a reducing agent, with one composition being an organic peroxide dissolved in a polymerizable substance (polyester resin and/or stabilizer, etc. dissolved as necessary). A method of reaction curing by contacting with a polyester resin and/or a stabilizer (if necessary). Reducing agents used in the present invention include tertiary amines, oxime compounds, thiuram compounds,
Examples include thiourea derivatives and metal salts. Third
Examples of the class amine include triethylamine, tripropylamine, tributylamine, triamylamine, ethylenediethanolamine, and N,N-dimethylparatoluidine. Oxime compounds include methyl ethyl ketone oxime,
Examples include methyl isobutyl ketone oxime, acetophenone oxime, and P,P'-dibenzoylquinone dioxime. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, diethylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea,
Examples include thiobarbituric acid. Metal salts include cobalt naphthenate, copper naphthenate,
Examples include vanadyl acetylacetonate and titanium acetylacetonate. Several kinds of these reducing agent components can be used in combination depending on the purpose. The amount of reducing agent used in the adhesive composition is 0.05 to 15% by weight, preferably 0.1 to 10% by weight. As mentioned above, the adhesive composition of the present invention has GA
Monomers and other polymerizable substances if necessary,
The essential ingredients are soluble polyester resin, organic peroxide, and reducing agent, but in addition, paraffin wax is used to increase surface hardening, and various antioxidants and polymerization inhibitors are added to improve stability. It is also possible to use known additives in combination. Furthermore, depending on the purpose, it is also possible to use plasticizers, fillers, thickeners, colorants, etc. Incidentally, the weight percentages of the proportions of each component used so far are the proportions in the entire composition that ultimately acts as an adhesive. In other words, when it is divided into two liquids, it is the ratio of the total of those two liquids. As mentioned above, the adhesive composition of the present invention is capable of bonding plastic film, metal foil, paper, cloth, etc. with one type, and is also capable of bonding polyester film, aluminum foil, etc., which were relatively difficult to bond in the past. The objective is to provide a new, high-performance adhesive that exhibits strong peel strength against, has excellent heat deterioration resistance, moisture deterioration resistance, and adhesion over a wide temperature range, and is highly flexible. This will greatly contribute to industry by improving productivity. <Examples> The present invention will be further explained by examples. Example 1 245 g of methoxypolyethylene glycol methacrylate (however, = 9), 245 g of methyl methacrylate (hereinafter abbreviated as MMA), commercially available polyester resin (trade name, Byron 500 Toyo Add 260 g of PET-500 (manufactured by Boseki Co., Ltd., hereinafter abbreviated as PET-500) and 4.5 g of paraffin with a melting point of approximately 50°C, and dissolve at 50°C.
A viscous liquid with a uniform viscosity of about 3000 cps (B-type viscometer, 25°C) was obtained. Divide this viscous liquid into two equal parts, and add organic peroxide cumene hydroperoxide to one viscous liquid.
18.5g, 0.75g of polymerization inhibitor hydroquinone monomethyl ether, and 12g of methacrylic acid were added, and composition No.
Composition No. 1-A was prepared, and 5.2 g of tetramethylthiourea, which is a reducing agent component, was added to the other viscous liquid which was divided into two to prepare Composition No. 1-B. Mix composition No. 1-A/No. 1-B at a ratio of 1:1, and apply the adhesive to an adherend (10 cm x 10 cm) so that the thickness of the adhesive is approximately
Apply it evenly to a thickness of 50 μm, sandwich it between 3 mm thick polyethylene plates, put a 1 kg load on it, and
It was cured for 2 hours in a constant temperature and humidity room at 50% RH. After that, it was cut into 25mm width and the 180 degree peel strength was measured using an Instron tensile tester at a peeling speed of 50mm/min.The result was 4.5Kg/25mm for the combination of polyester film/polyester film, and 4.5Kg/25mm for the combination of aluminum foil/aluminum foil. The peel strength was 4.5Kg/25mm, which was unimaginable with conventional adhesives. Note that initial curing was achieved in 15 minutes. Also No.1-
A/No. 1-B was mixed in a 1:1 ratio to make a cured product with a diameter of 38 mm and a thickness of 2 mm. When bent by hand, it did not break and returned to its original state when the force was removed. It exhibited flexibility not seen in reactive acrylic adhesives. The adhesion performance to various other adherends is summarized in Table 1, and it shows excellent adhesion performance to all the adherends. Example 2 Methoxypolyethylene glycol methacrylate (however = 23) 245g, MMA245g, intrinsic viscosity
0.73, molecular weight 18000-20000, melt viscosity 3000 poise commercially available polyester resin (trade name: Vylon 103,
(manufactured by Toyobo Co., Ltd.) and 4.5 g of paraffin with a melting point of approximately 50°C were added and dissolved at 50°C to obtain a viscous liquid with a uniform viscosity of approximately 12,000 cps (B-type viscometer, 25°C).
This viscous liquid was divided into two equal parts, 18.5 g of benzoyl peroxide and 0.75 g of hydroquinone monomethyl ether were added in the same manner as in Example-1, and Composition No. 2-
Make A and add N, N to the other viscous liquid divided into two parts.
- Adding 7.5 g of dimethyl para-toluidine to the composition
I made No. 2-B. When the peel strength of the polyester film/polyester film combination was measured in the same manner as in Example 1, a strong peel strength of 4.2 Kg/25 mm was obtained. The adhesion performance for various other adherends is summarized in Table 1. Example 3 Phenoxypolyethylene glycol acrylate (however = 6) 245g, MMA245g, Example-1
260 g of the same polyester resin PET-500 and 4.5 g of paraffin with a melting point of about 50°C were added and dissolved at 50°C to obtain a viscous liquid with a uniform viscosity of about 2800 cps (B-type viscometer, 25°C). This viscous liquid was divided into two equal parts, and 18.5 g of cumene hydroperoxide, 0.75 g of hydroquinone monomethyl ether, and 12 g of methacrylic acid were added to one of the viscous liquid to make composition No. 3-A. 2 g of 10% copper naphthenate in one viscous liquid;
Added 5.2 g of ethylene thiourea, composition No. 3-B
I made it. As in Example 1, the peel strength of the polyester film/polyester film combination was measured and a strong peel strength of 4.1 Kg/25 mm was obtained. The adhesion performance for various other adherends is summarized in Table 1. Example 4 Using No. 1-A/No. 1-B manufactured in Example-1, adhesive test pieces of polyester film/cotton canvas were made using the same adhesion method as in Example-1.
Moisture deterioration resistance at 95% RH and heat deterioration resistance at 110°C were measured. The results are shown in Table 2. With the composition of the present invention, no decrease in adhesive strength was observed in both tests, and in the heat deterioration test, the adhesive strength was actually higher, which was extremely high. It can be seen that it has excellent performance. For comparison, commercially available chloroprene rubber solvent type adhesive No. 7 used for adhesion of polyester film/paper, polyester film/cloth, etc.
The adhesive performance of the adhesive composition of the present invention was evaluated, and the adhesive strength became zero after 300 hours in both moisture deterioration resistance and heat deterioration resistance, and as shown in Table 2, it was found that the performance was significantly inferior to that of the adhesive composition of the present invention. . Example 5 Using No. 1-A/No. 1-B manufactured in Example-1, adhesive test pieces of polyester film/cotton canvas were made using the same adhesion method as in Example-1, and ±
In a thermostat at a predetermined temperature controlled at 1℃
The adhesive was allowed to stand for 30 minutes and its peel strength was measured at the same temperature. As a result, it was found that it exhibited good adhesion over a wide temperature range that was unimaginable with conventional adhesives. For comparison, commercially available chloroprene rubber adhesive No. 7, which is the same as Example 4, was evaluated, but it was confirmed that its performance was significantly inferior to that of the adhesive of the present invention. The results are summarized in Table 3. Example 6 Using No. 1-A/No. 1-B manufactured in Example-1, PVC film/PVC film, polyarylate film/polyarylate film were bonded using the same bonding method as in Example-1. As a result of measuring the peel strength of combinations such as rayon cloth/rayon cloth, cotton canvas/cotton canvas, stainless steel foil/stainless steel foil, iron foil/iron foil, etc., the results were as follows: Comparative Example No. 1, which was tested at the same time as a comparative example. Adhesive composition No. 1-A/No. 1-B of the present invention exhibited better strength than No. 4-A/No. 4-B in all combinations. The strength was measured in the same manner as in Example-1. The results are summarized in Table 4. Comparative example 1 MMA245g, 2-hydroxyethyl methacrylate 245g, acrylonitrile-butadiene rubber,
(USA, manufactured by BFGoodrich, Hiker 1072)
100g, add 4.0g of paraffin with a melting point of approximately 50℃, and heat at 50℃.
Dissolved with a uniform viscosity of approximately 3500 cps (B type viscometer,
A viscous liquid at a temperature of 25°C was obtained. Divide this viscous liquid into two equal parts,
Cumene hydroperoxide in one viscous liquid
15.5g, hydroquinone monomethyl ether 0.6g,
Add 10g of methacrylic acid to make composition No. 4-A.
4.3 g of tetramethylthiourea was added to the other viscous liquid divided into two to prepare Composition No. 4-B. When the peel strength of the polyester film/polyester film combination bonded together in the same manner as in Example 1 was measured, the strength was almost zero. Regarding other adherends, paper/paper resulted in paper breakage, which was no different from the adhesive of the present invention, but aluminum foil/aluminum foil, polyester film/cotton canvas, and aluminum foil/cotton canvas combinations resulted in paper tearing. The adhesive strength is significantly inferior compared to the composition of the present invention. Furthermore, regarding the flexibility of the cured product, when a cured product was prepared in the same manner as in Example 1 and bent by hand, it broke, and the flexibility of the composition of the present invention could not be obtained. The results are summarized in Table-1. Comparative Example 2 245 g of MMA, 245 g of 2-hydroxyethyl methacrylate, 260 g of PET-500, and 4.5 g of paraffin with a melting point of about 50°C were added and melted at 50°C to obtain a uniform viscosity of about 3400 cps (B-type viscometer, 25°C). A viscous liquid was obtained.
This viscous liquid was divided into two equal parts, and 18.5 g of cumene hydroperoxide, 0.75 g of hydroquinone monomethyl ether, and 12 parts of methacrylic acid were added to one of the viscous liquid to prepare composition No. 5-A. 5.2 g of tetramethylthiourea was added to one of the viscous liquids to prepare Composition No. 5-B. When the peel strength of the polyester film/polyester film combination was measured in the same manner as in Example 1, the peel strength was 0.2 Kg/25 mm, which was a lower value than the composition of the present invention. The adhesion to other adherends was the same as in Comparative Example-1.
Except for paper adhesion, the results were significantly inferior to those of the composition of the present invention. The results are summarized in Table-1. Comparative Example 3 Add 192g of PET-500 to 360g of MMA and dissolve at 50℃, then cool to room temperature and add methacrylic acid to the viscous liquid.
102g, tris(dimethylaminomethyl)phenol 102g, triallyl cyanurate 37g, and dimethyl para-toluidine 6.4g were added to form a uniform viscous liquid No. 6.
-I made B. Homogeneous solution No. 6-A was prepared by dissolving 5 parts of polymethyl methacrylate and 5 g of benzoyl peroxide in 100 g of ethyl acetate. Coat No. 6-A uniformly on a polyester film in advance, evaporate the ethyl acetate at room temperature, and then apply No. 6-B on another polyester film.
When the peel strength was measured by overlapping the coated material to a thickness of 50 μm and adhering it under the same conditions as in Example 1, it was 0.4 Kg/25 mm, which was compared to the composition of the present invention.
It showed only a low value of intensity. The adhesion to other adherends was also similar to Comparative Example 1, and was significantly inferior to the composition of the present invention. In addition, when combining various types of adherends, No. 6-A was applied to the polyester film and aluminum foil sides. Example 7 Methoxydiethylene glycol methacrylate
490g, same polyester resin as Example-1
260g of PET-500, 4.5g of paraffin with a melting point of approximately 50℃
Add and dissolve at 50℃ to a uniform viscosity of approximately 4000cps.
A viscous liquid of (B-type viscometer: 25°C) was obtained. This viscous liquid was divided into two equal parts, and 18.5 g of cumene handroperoxide, 6 g of diethylaminoethyl methacrylate, and 0.75 g of hydroquinone monomethyl ether were added to one viscous liquid to prepare composition No. 8-A, which was divided into two equal parts. 5.2 g of tetramethylthiourea and 2 g of 10% copper naphthenate, which are reducing agent components, were added to the other viscous liquid to prepare composition No. 8-B. When the peel strength was measured for the polyester film/polyester film combination in the same manner as in Example-1, it was found to be 3.9.
A strong peel strength of Kg/25mm was obtained. Adhesion properties to other various adherends are summarized in Table 1.

【table】

[Table] Adherent: Polyester film/cotton canvas (details are described above) Blank: Apply adhesive to a 10cm x 10cm polyester film to a thickness of 50μm, overlap with cotton canvas, and then apply adhesive to a thickness of 3mm. A load of 1 kg is applied between the polyethylene plates (perforated polyethylene plates with a diameter of 3 mm in the case of rubber adhesive) and cured for 24 hours in a constant temperature and humidity room at 23°C and 50% RH. It was then cut into 25mm width pieces and tested at a peeling speed of 50 using an Instron tensile tester.
Peel strength is measured in mm/min. Moisture deterioration resistance: Test piece prepared under the same conditions as the blank above (width 25
mm, length 10cm) in a constant temperature and humidity chamber at 60℃ and 95% RH for 100 and 300 hours, respectively, and after taking it out at 23℃,
After leaving it in a constant temperature and humidity room at 50% RH for 30 minutes and lowering the temperature, peel strength was measured under the same conditions as the blank. Heat deterioration resistance: Test piece prepared under the same conditions as the above blank (width 25
100 mm, length 10 cm) each in a thermostat at 110℃,
It was left to stand for 300 hours, and after being taken out, it was left in a constant temperature and humidity room at 23℃ and 50% RH for 30 minutes, and after the temperature was lowered, the peel strength was measured under the same conditions as the blank.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) Contains 20 to 94% by weight of a polymerizable substance having at least one unsaturated double bond in the molecule, and contains a compound having the general formula CH ₂ =CR ₁ -CO( −OCH ₂ CHR ₂ −)
nOR ₃ (However, R ₁ and R ₂ are hydrogen or methyl groups,
R ₃ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a carbon number 1
a phenyl group having ~4 alkyl substituents,
5 to 70% by weight of a polymerizable substance (n represents an integer of 2 to 27); (B) a polyester resin 5 soluble in the polymerizable substance;
~60% by weight, (C) 0.1 to 20% by weight of an organic peroxide, and (D) 0.05 to 15% by weight of a reducing agent capable of generating radicals upon contact with the organic peroxide. Adhesive composition.