JPS6024825B2 - photosensitive adhesive composition - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photosensitive adhesive composition, and more particularly to a photosensitive adhesive composition with excellent adhesive strength that cures and adheres extremely quickly when irradiated with light, particularly ultraviolet rays. Adhesives are required to have various performances depending on the type of adherend and application. Particularly in fields that require precision assembly, such as precision machinery and precision crafts, deformation and distortion caused by heat curing are often disliked, and the complicated manual work makes it difficult to rationalize and save labor, reducing production efficiency. The problem is that it is low. From this point of view, there has been a demand for the development of an adhesive that can be used quickly and has excellent adhesive strength for non-absorbent objects that dislike heat curing. Photocurable resins, which have recently been actively put into practical use in inks, clear varnishes, paints, etc., have attracted attention as a new adhesive that satisfies these demands. However, conventional photosensitive adhesives using photocurable resin as a base vehicle have not been able to satisfy both rapid curing properties and high adhesive strength. For example, a photosensitive adhesive whose main component is an addition reaction product of an epoxy resin and an 8-unsaturated acid is rapidly cured by ultraviolet irradiation, but has a problem of low adhesive strength. Furthermore, although photosensitive adhesives mainly composed of liquid polybutadiene or liquid polysobrene and acrylic acid ester have excellent adhesive strength when irradiated with ultraviolet rays, they require a relatively long time for complete curing. Therefore, the present inventors conducted repeated research in order to obtain a photosensitive adhesive composition that cures and adheres extremely quickly when irradiated with light, particularly ultraviolet rays, and has excellent adhesive strength, and as a result, the present invention was completed. That is, the present invention is directed to a polyoxyalkylene bisphenol A derivative having a terminal hydroxyl group, a polyisocyanate compound, and a hydroxyl group-containing acrylate and/or methacrylate (hereinafter abbreviated as (meth)acrylate). Two or more acryloyl groups and/or methacryloyl groups (hereinafter (meth)) in one molecule
Acrylic urethane resin and/or methacrylic urethane resin [1] (hereinafter referred to as (abbreviated as acryloyl group))
(abbreviated as meth) acrylic urethane resin), said (meth)
(Meth)acrylate having a hydroxyl group copolymerizable with the terminal unsaturated group introduced into the acrylic urethane resin [1]

The present invention relates to a photosensitive adhesive composition containing [0] and a photosensitizer [m] as main components. Details are provided below for each of the resin components that can be used in the present invention. The polyoxyalkylene bisphenol A derivative according to the present invention is a compound containing polyoxyalkylene bisphenol A or polyoxyalkylene bisphenol A in its chemical structure and having a hydroxyl group at the terminal. Polyoxyalkylene bisphenol A is obtained by reacting bisphenol A with alkylene oxide. Suitable alkylene oxides that can be used include, for example, ethylene oxide and propylene oxide. The polyoxyalkylene bisphenol A useful in the present invention has the following formula [i} or [o}
It is possible to express it as [RI in formula {i} or 'o} is an alkylene group having 2 to 4 carbon atoms, X is a halogen or methyl group, a is an integer of 1 to 2, m and n are each is an integer that is at least 1, and the sum of m and n is an integer from 2 to 8. ] The sum of m and n in the above formula {i} or (b) is determined from the number of moles of alkylene oxide reacted with the hydroxyl group of bisphenol A. As the number of moles of alkylene oxide added increases, the amount of resin increases. Flexibility and elongation are improved, but adhesive strength is reduced and the curing speed is slowed down.Polyoxyalkylene bisphenol A derivatives having a terminal hydroxyl group in the present invention include those represented by the above formulas [i} and 'o}. In addition to the expressed polyoxyalkylene bisphenol A, it also includes condensation reaction products of polycarboxylic acids and/or their acid anhydrides and the above polyoxyalkylene bisphenol A, and the polyoxyalkylene bisphenol A pairing component in the condensation reaction is also included. It is desirable that the molar ratio is 3 to 2 or more. Here, the acid anhydride is equivalent to 2 moles of carpoxyl groups. If the molar ratio is 4.0 molar than 3 to 2, the resulting condensation reaction product The molecular weight of the product is too high, which causes inconvenience in subsequent handling, or it becomes a resin with a terminal carboxylic acid group, making it impossible to obtain the target compound of the present invention.In addition, the condensation reaction product and the above polyoxyalkylene A mixture of bisphenol A and bisphenol A in any proportion can also be used. Examples of the brewing ingredients used include malonic acid, succinic acid, succinic anhydride, glutaric acid, adipisoic acid, pimelic acid, suberic acid, Aliphatic saturated dibasic acids or saturated dibasic acid anhydrides such as azelaic acid and sebacic acid, aliphatic unsaturated dibasic acids or unsaturated acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, etc. Examples include aromatic dibasic acids or dibasic acid anhydrides such as saturated dibasic acid anhydrides, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc.Production of the above polyoxyalkylene bisphenol A derivative style In the above dibasic acid and/or dibasic acid anhydride etc.
In addition to the first brewing component, it is possible to use small amounts of a second polycarboxylic acid, such as trimellitic anhydride. This second acid can be aromatic or aliphatic, and can be saturated or unsaturated. In addition to the first glycol component of the polyoxyalkylene bisphenol, in addition to the first glycol component of the polyoxyalkylene bisphenol, the same machine
It is possible to use a small amount of a glycol component having 2 or 12 carbon atoms. This second glycol includes, in addition to so-called aliphatic and cycloaliphatic glycols, polyether glycols such as triethylene glycol and glycidyl ethers such as phenylglycidyl ether. These brewing ingredients and polyoxyalkylene bispheres/-A conductors can be used alone or in combination of two or more. The following are representative examples of the polyisocyanate compounds used in the present invention. Namely, tolylene diisocyanate, diphenylmethane-4,4'-isocyanate, 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,6- Hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, hydrogenated tolylene diisocyanate, partially carbodiimidized diphenylmethane-4, 4′
diisocyanates, or dimers of these diisocyanates, or addition compounds of these diisocyanates and active hydrogen compounds, i.e., ethylene glycol, propylene glycol, tetramethylene glycol.
Neobentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, bentaerythritol, bisphenol A. These are adducts of ethylene oxide adducts, bisphenol A/propylene oxide adducts, etc. and the above diisocyanates. These polyisocyanate compounds can be used alone or in combination of two or more. The amount of polyisocyanate compound used is 1.8 to 5, preferably 2 to 3 isocyanate groups per hydroxyl group of the polyoxyalkylene bisphenol A derivative used. There are 1 isocyanate group per 1 hydroxyl group of the polyoxyalkylene bisphenol A derivative. When the amount is less than the milk sphere, the viscosity of the resulting resin is too high, resulting in poor processability. On the other hand, it has been found that when the number is more than 5, no further improvement is seen in the adhesive strength of the resulting adhesive composition. As the hydroxyl group-containing (meth)acrylate used in the present invention, compounds having the following general formulas are exemplified. [R2 in the formula 1, 8, 'ho' or Takenaka is a hydrogen atom or a methyl group, R3 is an alkylene group having 2 to 10 carbon atoms, and R4 is a hydrogen atom or a carbonized group having 1 to 6 carbon atoms. It is a hydrogen group, p is an integer of 1 to 3, and q is an integer of 1 to 2. ] These hydroxyl group-containing (meth)acrylates can be obtained by known methods. The integer p in the above formula is determined by the number of moles of alkylene oxide or glycol used per mole of (meth)acrylic acid. If more than about 3 moles of alkylene oxide or glycol are used, the resulting resin will have a low heat strain temperature and a reduced adhesive strength. Typical hydroxyl group-containing (meth)acrylates that can be used include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate polyoxyethylene
(meth)acrylate, polyoxyethylene '31 (meth)acrylate, polyoxypropylene [21 (meth)acrylate, polyoxypropylene lake (meth)acrylate, trimethylolethane mono(meth)acrylate, trimethylolethane di(meth)acrylate acrylate,
Trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin mono(meth)acrylate , glycerin di(meth)acrylate, etc. In addition, other monoepoxy compounds such as epichlorohydrin, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidyl (
(Meth)acrylic acid adducts such as meth)acrylate can also be used. The above hydroxyl group-containing (meth)acrylate compound {0 can be used either as a single compound or as a mixture of two or more compounds. Hydroxyl group-containing (meth)acrylate compound used {q
The number of moles c of (number of hydroxyl groups in one molecule = z pieces) is 1 mole of polyoxyalkylene bisphenol A derivative style (number of hydroxyl groups in one molecule = x pieces) and polyisocyanate compound t
B}' (number of isocyanate groups in one molecule = y pieces) is generally expressed by the following formula from the amount b moles used. cZ(bxy-x)/z The (meth)acrylic urethane resin [1] according to the present invention can be produced by a known method. Typical production methods include a one-stage reaction method or a two-stage reaction method in which two components are first reacted and then the resulting prepolymer is reacted with a third component. This resin can be manufactured as a melt without using any solvent,
Alternatively, it can be carried out in the presence of a suitable solvent or a vinyl compound capable of polymerizing with the terminal unsaturated group introduced into the meth)acrylic urethane resin. In the one-stage reaction method, first, polyoxyalkylene bisphenol A derivative W is melted, and hydroxyl group-containing (meth)acrylate {q is added to this melt. The polyisocyanate compound is then slowly added and the reaction temperature is increased to about 125°C. Next, the desired (meth)acrylic urethane resin can be obtained by carrying out the reaction while maintaining this reaction temperature until the isocyanate groups in the reaction mixture become substantially zero. When a solvent or a vinyl compound is used in the reaction mixture, all components are added and dissolved in the solvent or vinyl compound, and the resulting reaction mixture is maintained at a temperature of about 50°C to about 8°C until the reaction is complete. do. The actual temperature used can vary depending on the reaction reagents used, reaction time, and the like. The (meth)acrylate [U] having a terminal unsaturated group and a polymerizable hydroxyl group introduced into the (meth)acrylic urethane resin [1] used in the present invention has the above-mentioned general formula, 8, and N, preferably, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyoxyethylene [2} (meth)acrylate, polyoxypropylene (2) (meth)acrylate, ) acrylate, polyoxyethylene leg (meth)acrylate, polyoxypropylene '3} (meth)acrylate,
Examples include trimethylolpropane mono(meth)acrylate, bentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, and glycerin mono(meth)acrylate. In addition, 3-chloro-2-hydroxypropyl (meth)acrylate and the like can also be used. These can be used alone or in the form of a mixture of two or more.
Moreover, a part of the amount used can be replaced by (meth)acrylate or aromatic vinyl compound having no hydroxyl group. (Meth)acrylic urethane resin [1] used in the present invention and (meth)acrylate having a hydroxyl group [
The usage ratio (weight) with 0) is preferably 30:70 to 95:5, more preferably 50:50 to 80:20. The photosensitizer [m] used in the present invention may be a known one, such as ketone sensitizers such as penzophenone, p-methylbenzophenone, p-chlorobenzophenone, Michler's ketone, and acetophenone, and benzoin. , benzoin methyl ether, benzoin ethyl ether, benzoin isop. Penzoin sensitizers such as pyl ether, benzoin isobutyl ether, Q-allylbenzoin, Q-chlorobenzoin, anthraquinone, 2-methylanthraquinone, 11-chloroanthraquinone, p-benzoquinone,
Quinone sensitizers such as 1,4-naphthoquinone, sulfide sensitizers such as phenyl disulfide and tetramethylthiuram monosulfide, sulfonyl chlorides such as 8-naphthalene sulfonyl chloride and p-chlorobenzenesulfonyl chloride. Nitro compound sensitizers such as 2-nitrofluorene and 5-nitroacenaphthene, halogenated hydrocarbon sensitizers such as tetrapromomethane, and thioxanthone sensitizers such as 2-chlorothioxanthone , azo sensitizers such as azobisisobutyronitrile, and composite sensitizers that are a combination of various sensitizers. The amount of these photosensitizers used can vary over a wide range, but from the viewpoint of adhesive strength and curing speed, it is preferably from 0.5 to 2 in the total adhesive composition.
Preferably, the weight percent is . The adhesive body referred to in the present invention must be made of a light-transmissive material such as transparent glass or transparent plastic on the light-irradiated side, but there is no particular restriction on the non-light-irradiated side, such as glass,
This includes metals, plastics, paper, printed paper, plywood, wood, cloth, etc. As described above, the photosensitive adhesive composition referred to in the present invention has substantially two
(meth)acrylic urethane resin [1] having at least three (meth)acryloyl groups, and a (meth)acrylic urethane resin having a hydroxyl group copolymerizable with the terminal unsaturated group introduced into the (meth)acrylic urethane resin. acrylate

[0] and photosensitizer [
m], but resins such as alkyd resins, polyester resins, and epoxy resins, viscosity-adjusting solvents, plasticizers, and curing accelerators can be added as necessary. The present invention will be explained in more detail below using production examples and examples. All parts in the examples are parts by weight. Production example 1 2 moles of propylene oxide adduct of bisphenol A was added to 2.
0 mol and 1.01 mol of maleic anhydride were placed in a flask and raised to 22,000 in a nitrogen stream. After continuing the reaction while keeping the reaction temperature at this temperature until the acid value became 8 or less, 0.05% by weight (0.40 parts, 0.0037 mol) of hydroquinone was added to the total amount of the polyester glycol. Prepare. This polyester glycol is further cooled to 100°C, mixed with 2.02 moles of 2-hydroxyethyl acrylate, and then dehydrated under reduced pressure while maintaining the temperature at 95°C to reduce the amount of water to 0.0% by weight or less. . After dehydration, it was cooled to 75°C, and while blowing air, 2.0 mol of tolylene diisocyanate was gradually added dropwise, reacted at a temperature of 75°C to 115°C for 496 hours, and further aged at 125°C to 128°C for 5 hours to remove residual NCO. The reaction was completed after confirming that the percentage was 0.1% by weight or less. In this way, a pale yellow transparent solid acrylic urethane resin was obtained. Acid value (AV) = 4.9, hydroxyl value (OHV)
) = 21.0, NCO% (weight) = 0.08 Production Example 2 In place of the 2 mole adduct of bisphenol A and propylene oxide in the reaction of Production Example 1, a 2 mole adduct of bisphenol A and ethylene oxide was used. The same reaction was carried out except that 2-hydroxyethyl methacrylate was used instead of -hydroxyethyl acrylate to obtain a methacrylic urethane resin as a pale yellow transparent solid. AV 5.6, OHV=18.6, NCO%=0. Female Production Example 3 A completely similar reaction was carried out except that instead of the 2-mol adduct of bisphenol A and propylene oxide in the reaction of Production Example 1, a 4-mol adduct of bisphenol A and propylene oxide was used to produce a pale yellow transparent solid acrylic urethane resin. I got it. AV = 6.00 HV = 12.1, NCO% = 0.1 Production Example 4 Exactly the same reaction as in Production Example 1 except that adipic acid was used instead of maleic anhydride was carried out to produce acrylic urethane as a pale yellow transparent solid. Resin was obtained. AV=4. OHV = 10.3 NCO% = 0.03 Production Example 5 Polyester glycol 1.05 produced using a 6 mole adduct of bisphenol A with propylene oxide instead of the 2 mole adduct of bisphenol A with propylene oxide in Production Example 1. mol and 4.04 mol of 2-hydroxyethyl acrylate are placed in a flask and dehydrated under reduced pressure while maintaining the temperature at 95°C to reduce the amount of water to 0.00% by weight or less. After dehydration and cooling to 0.7%, adduct polyisocyanate of trimethylolpropane and hexamethylene diisocyanate {2016 parts as a 75% ethyl acetate solution (trade name Coronate HL, manufactured by Nippon Polyurethane ■)} while blowing air. Gradually drop 0 mol of 75q0~
The reaction was carried out at a temperature range of 85°C for 40 minutes. Next 125q
The product was aged for 4 hours while removing ethyl acetate from Coronate HL at 0 to 128 qo, and the reaction was determined to have ended when it was confirmed that the residual NCO% was 0.1% by weight or less. Further, residual ethyl acetate was removed under reduced pressure to obtain a pale yellow transparent liquid acrylic urethane resin. AV=1.7, OHV=11.5
NCO%=0.071·6 A flask was charged with 1.0 mol of tolylene diisocyanate and 0.15 part (0.0014 mol) of hydroquinone, and the temperature was raised to 7,000. Next, while blowing air, 1.0 mol of 2-hydroxyethyl acrylate was gradually added dropwise to 70 qo to 80 qo.
The reaction was carried out at o0 for 1 hour. The mixture was further aged at 80° C. for 1 hour to prepare an acrylic urethane polymer with terminal NCO having a residual NCO of 14.5% by weight. Meanwhile, in another flask, add 1 mol of propylene oxide adduct of pisphenol A.
．． 0.5 mol was charged and dehydrated under reduced pressure while maintaining the temperature at 95°C to reduce the water content to 0.00% by weight or less. After dehydration, the acrylic urethane prepolymer 2.0 with terminal NCO prepared previously was cooled to 760°C and air was blown into it.
The reaction was carried out for 1 hour in a temperature range of 7500 to 115 qo while gradually dropping the mol. Furthermore, 125 qo to 128 qo
After aging for 4 hours, it was confirmed that the residual NCO% was 0.1% by weight or less, and a pale yellow transparent solid acrylic urethane resin was obtained. AV=1.4, OHV=20. Kame NCO%
= 0.08 Production Example 7 558 parts (3 epoxy equivalents) of the epoxy resin Epikote 828 (epoxy equivalent weight 186) manufactured by Shell Co. and 0.3 parts (0.0035 mol) of hydroquinone were placed in a flask and heated to 11 pm while blowing air. The temperature rose to Next, 3.0 moles of acrylic acid and 3.9 parts (0.015 moles) of DMP-30 (tridimethylaminomethylphenol, manufactured by Rohm and Haas) were uniformly mixed in advance at room temperature and then added to the above epoxy resin. The mixture was gradually added dropwise and the reaction was carried out for 1 hour at 110qC to 120q○ while cooling the flask. After further aging at 12,000 for 4 hours, it was confirmed that the acid value had become 5 or less, and a pale yellow transparent liquid epoxy acrylic resin was obtained. AV=0.47, oxirane oxygen%
(Weight) = 0.03 Production Example 8 0.75 mol of the terminal NCO acrylic urethane prepolymer prepared in Production Example 6 was heated to 8,000 mol of trimethylolpropane o. While gradually dropping 25 mol, the reaction was carried out at 80°C to 90q0 for 30 minutes. Further aged for 3 hours at 110 o'clock to 12 o'clock to remove residual NC.
It was confirmed that O% was 0.4% by weight or less, and an acrylic urethane resin as a pale yellow transparent solid was obtained. AV=1. FuO
HV=23.0, NCO%=0.37 Example 1 A photosensitive adhesive composition was prepared by adding 5 parts of penzoin isobutyl ether as a sensitizer to the resin component and monomer component of the first notation. was prepared. The photosensitive adhesive layer with a thickness of 2 mm x 2 mm thick was coated using a wire coater on a 5-sided transparent glass slope that had been degreased with acetone, and a 5-sided layer with a thickness of 5 mm was applied as an adherend on top of the photosensitive adhesive layer. After stacking the transparent glass plates and pressing the glass plates lightly to confirm that the adhesive layer is uniform, apply ultraviolet rays for 1 second from a distance of 80° using a Fox W high-pressure mercury lamp (manufactured by Nippon Battery). It was irradiated to harden and bond. The tensile breaking strength of the obtained test piece (tensile speed: 5 min/min) was measured using an automatic tensile testing device (manufactured by Shimadzu Corporation). The obtained results are the first
Shown in the table. The measured value is the average value of 5 test pieces. still,
For comparison, photosensitive adhesive compositions other than those of the present invention were tested in the same manner, and the results are also shown in Table 1. Table 1 Example 2 6 parts of the resin synthesized in Production Example 1 and 4 parts of 2-hydroxyethyl acrylate were added with 5 parts of penzoin isobutyl ether as a sensitizer to form a photosensitive adhesive. A drug composition was prepared. Apply an adhesive layer of 1 inch wide x 2 inches thick x 20 inches thick using a wire coater on a glass plate with a thickness of 5 mm that has been degreased with acetone, and overlay various metal plates or various plastic plates on top of it. Then, after confirming that the adhesive layer was uniform by lightly pressing the objects together, the adhesive layer was cured in the same manner as in Example 1, and the tensile breaking strength was measured. The results obtained are shown in Table 2. Note to Table 2) Ki 1 Degreased with acetone ★ 2 Washed with a neutral detergent family manufactured by Kao Seiki Co., Ltd. Example 3 The photosensitive adhesive composition prepared in Example 2 was applied onto printed art paper. Example 1: Coated with a wire coater to a thickness of 10 mounds, laminated an oxidized 12 molar polypropylene film thereon, and then lightly pressed the adherends together to confirm that the adhesive layer was uniform. It was cured and glued in the same way.

Claims (1)

[Claims] Primary formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is an alkylene group having 2 to 4 carbon atoms, and X is a halogen or a methyl group, a is an integer of 1 to 2, m and n are each an integer of at least 1, and the sum of m and n is an integer of 2 to 8), and a compound represented by the formula (a) and/or (b)
A polyoxyalkylene bisphenol A derivative (A) selected from the group consisting of a compound having a terminal hydroxyl group which is an ester of a polycarboxylic acid or its anhydride of a compound represented by (Meth)acrylic urethane resin [I ]
and (meth)acrylate [II] having a hydroxyl group copolymerizable with the terminal unsaturated group introduced into the (meth)acrylic urethane resin [I] and a photosensitizer [III] as main components. A photosensitive adhesive composition containing. 2 In formula (a) or (b), alkylene group R^1
The photosensitive adhesive composition according to claim 1, wherein is an ethylene group or a propylene group. 3. The photosensitive adhesive composition according to claim 1, wherein the polycarboxylic acid or its anhydride is a dicarboxylic acid or a dicarboxylic acid anhydride. 4 In formula (a) or (b), the sum of m and n is 2
6. The photosensitive adhesive composition according to claim 1, which is 5 Polyoxyalkylene bisphenol A derivative (A
) is an ester obtained by condensing a compound represented by formula (a) and/or (b) with a polycarboxylic acid at a molar ratio of 3:2 or more. Composition. 6. The photosensitive adhesive composition according to claim 1, wherein the polyisocyanate compound (B) is tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate or hexamethylene diisocyanate. 7 Having a hydroxyl group-containing (meth)acrylate (c) constituting the (meth)acrylic urethane resin [I] and a hydroxyl group that can be copolymerized with the terminal unsaturated group introduced into the (meth)acrylic urethane resin [I] The photosensitive adhesive composition according to claim 1, wherein the (meth)acrylate [II] is a compound represented by the following formula (c), (d), (e) or (f); There are chemical formulas, tables, etc. ▼ (R^2 in formula (c), (d), (e), or (f) is a hydrogen atom or a methyl group, and R^3 is an alkylene group having 2 to 10 carbon atoms. , R^4 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and p is 1 to 3
is an integer of 1 to 2, and q is an integer of 1 to 2. )8 The (meth)acrylic urethane resin [I] has a ratio of hydroxyl groups of the polyoxyalkylene bisphenol A derivative (A) to isocyanate groups of the polyisocyanate compound (B) of 1:1.8 to 5, and ii The number of moles (c) of the hydroxyl group-containing (meth)acrylate (C) (number of hydroxyl groups in one molecule = z pieces) is the number of moles (c) of the boroxyalkylene bisphenol A derivative (A) (number of hydroxyl groups in one molecule = x
From 1 mole of polyisocyanate compound (B) (number of isocyanate groups in 1 molecule = y) and b mole, the following formula
The photosensitive adhesive composition according to claim 1, which is obtained by reacting in accordance with c≧(b×y−x)/z. 9 The weight ratio of (meth)acrylic urethane resin [I] and (meth)acrylate [II] having a hydroxyl group copolymerizable with the terminal unsaturated group introduced into the resin is 30:7.
The photosensitive adhesive composition according to claim 1, wherein the ratio is 0 to 95:5. 10. The photosensitive adhesive composition according to claim 1, wherein the content of the photosensitizer [III] is 0.5 to 20% by weight based on the total adhesive composition. 11 Dicarboxylic acid is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid,
The photosensitive adhesive composition according to claim 3, which is a compound selected from the group consisting of itaconic acid, phthalic acid, isophthalic acid and terephthalic acid. 12. The photosensitive adhesive composition according to claim 3, wherein the dicarboxylic anhydride is a compound selected from the group consisting of succinic anhydride, maleic anhydride, and phthalic anhydride. 13 Hydroxyl group-containing (meth)acrylate (C) and (meth) composing (meth)acrylic urethane resin [I]
The (meth)acrylate [II] having a hydroxyl group copolymerizable with the terminal unsaturated group introduced into the acrylic urethane resin [I] is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate ,
Polyoxyethylene (2) (meth)acrylate, polyoxypropylene (2) (meth)acrylate, polyoxyethylene (3) (meth)acrylate, polyoxypropylene (3) (meth)acrylate, trimethylolpropane mono (meth) ) acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, glycerin mono(meth)acrylate and 3-chloro-2-hydroxypropyl(meth)acrylate. The photosensitive adhesive composition according to item 7. 14 The weight ratio of (meth)acrylic urethane resin [I] and (meth)acrylate [II] having a hydroxyl group copolymerizable with the terminal unsaturated group introduced into the resin is 50:
The photosensitive adhesive composition according to claim 9, wherein the ratio is 50 to 80:20.