JPH0232157A - Photo-setting composition and laminate using said composition as adhesive layer - Google Patents

Abstract

PURPOSE:To obtain a composition, consisting of a specific mercapto group- containing polymer, polyene and photopolymerization initiator and useful as adhesives, coatings and sealants requiring water and moisture resistance. CONSTITUTION:A composition obtained by blending a mercapto group-containing polymer without ester bond with a polyene without ester bonds and a photopolymerization initiator. The resultant photo-setting composition is interposed as an adhesive layer to provide a laminate consisting of both or one thereof capable of transmitting active rays of light.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a curable composition comprising a polyene, a mercapto group-containing polymer, and a photopolymerization initiator, and particularly relates to a curable composition comprising a polyene, a mercapto group-containing polymer, and a photopolymerization initiator. Useful as adhesives, paints, and sealants.

(Prior art) It is well known that polyenes and polythiols form polymers upon irradiation with actinic rays (J, ^va, c
heta, soc, + vol. 10, p. 993 (1948)
] By changing the chemical equivalent of the carbon-carbon unsaturated double bond of poporin and the mercapto group of polythiol, or by changing the number of functional groups of polyene and boritiol, various cured products ranging from elastomer to resin can be obtained. .

(Problems to be Solved by the Invention) Most of the polythiols used above are polyhydric alcohol esters of thioglycolic acid and thiopropionic acid, which are disclosed in Japanese Patent Publication No. 47-3269. However, since these substances have a low molecular weight, the viscosity of the composition formed in combination with polyene is very low, and they cannot be used as adhesives, paints, sealants, etc. in areas where thickness is required. Furthermore, since they have ester bonds in their molecules, cured compositions using these polythiols have the disadvantage that they are easily hydrolyzed in high humidity conditions, resulting in softening or elution. Naturally, this phenomenon is also observed when there is an ester bond within the polyene molecule. As a method for increasing the viscosity, as disclosed in Japanese Patent Publication No. 571,535, there is a method in which a mercapto group-containing polymer obtained by reacting polythiol and polyepoxide with an excess of polythiol is used as one component of the composition. Yes, but.

Even in this report, the above-mentioned ester group-containing polythiol is used, so the problem of hydrolysis is not solved.

An object of the present invention is to provide a photocurable composition comprising a mercapto group-containing polymer, a polyene, and a photopolymerization initiator, whose viscosity can be easily controlled over a wide range, and which has excellent water and moisture resistance. .

(Means for Solving the Problems) That is, the present invention is a photocurable composition comprising a mercapto group-containing polymer having no ester bond, a polyene having no ester bond, and a photopolymerization initiator. In the composition of the present invention, the mercapto group-containing polymer comprises (1) a polyepoxide having no ester bond;
The molar ratio of all mercapto groups to all epoxy groups is 1
．． 1 to 100, or (2) a polyene that does not have an ester bond and a total of mercapto groups for all of its carbon-carbon unsaturated double bonds. It is preferably a reaction product with a polythiol having no ester bond and having a molar ratio of 1.1 to 100.

The mercapto group-containing polymer obtained from polyepoxide and polythiol in (1) above has a repeating unit represented by the following formula (1), has an -SH group at the end, and has a molecular weight of 350 to 500,000. .

H C1IH2,1-3-... CI) (In the formula, t, w and ) The above mercapto group-containing polymer has an epoxy group of a polyepoxide having no ester bond represented by the -catalytic formula (U), and an epoxy group represented by the formula (I [[)]. It can be obtained by reacting the mercapto group of polythiol.

R+Cll-CL) -...(II'1\1 (However, R has the same meaning as formula (r), and m represents an integer of 2 or 3.) H5+Ct Hzt-A+i-C, HzxS)l"
” (III) (However, t, W, X, A are the above formula CI]
Same as . ) This reaction may proceed as a sequential reaction.

Typical examples of mercapto group-containing polymers obtained in this manner include those represented by the following formulas.

H3-C! H4-3-CtHa-5-C1l z-CO
-C8t-0+Cl t +-0-CHz-H CH-CHz 5-C2H45-C2H4-3R layer CHz-CIhCHz-5+CJ4-0 +r c, +
4. - SH Des H H (However, U is an integer of 1 to 950) Examples of the polyepoxide represented by the above general formula (II) include bisphenol A epoxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether,
g) Nocerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol polyglycidyl ether, bisphenol S-type epoxide, dicyclopentadiene phenolic polymer epoxy resin, bisphenol Examples include, but are not limited to, F-type epoxide, brominated bisphenol F-type epoxide, hydrogenated bisphenol A-type epoxide, and tris(2°3-epoxypropyl) isocyanurate.

Also, a mixture of two or more of these may be used.

In addition, examples of the polythiol represented by the above general formula (I [ etc., but the polyvalent thiols are not limited to these. Further, a mixture of two or more of these may be used, and particularly preferred ones have a viscosity of 1 to 10. It is OO0cps.

Synthesis of the mercapto group-containing polymer using the above polyepoxide and polythiol is carried out by mixing and stirring the two at a temperature of 0° C. or higher.

In addition, it is also possible to use a catalyst if necessary, and an example of this can be found in "Thermosetting Resins", Vol. 2, p. 140 (1
These include tertiary amines and tertiary phosphines, such as those listed in 981). The molar ratio of mercapto group to epoxy group is preferably 1.1 to 100 (mercapto group/epoxy group). Particularly preferably 1.4 to 20. If the molar ratio is less than 1.1, gelation and loss of mercapto groups occur. When the molar ratio exceeds 100, no modification by epoxide is observed. Further, by changing the molar ratio, the viscosity of this mercapto group-containing polymer can be adjusted freely over a very wide range. In addition, since this reaction has an excess of mercapto groups, the products are i) unreacted polythiol, ii) one molecule of polyepoxide reacted with polythiol, and iii) polyepoxide- In most cases, it is obtained in the form of a mixture of polythiol reactants as repeating units.

Therefore, if you want to obtain a single compound from among these, separation and purification may be required.

The mercapto group-containing polymer obtained from the polythiol and polyene in (2) above is obtained by reacting the mercapto group of the polythiol represented by the formula (I) with the carbon-carbon unsaturated double bond of the polyene having no ester bond. You can get it by doing this.

The polyenes used here include divinylbenzene, divinyltoluene, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl Ether, pentaerythritol tetraalyl ether, ethylene glycol di(meth)allyl ether, propylene glycol di(meth)allyl ether, butylene glycol di(meth)allyl ether, polyethylene glycol di(meth)allyl ether, polybropyrine glycol Di(meth)allyl ether, polybutylene glycol di(meth)allyl ether, di(meth)allyl ether of glycol which is a block or random copolymer of ethylene oxide and propylene oxide, block or random copolymer of ethylene oxide and tetrahydrofuran. Di(meth)allyl ether of a certain glycol, di(meth)allyl ether of a glycol which is a block or random copolymer of propylene oxide and tetrahydrofuran, di(meth)allyl ether of bisphenol A, bisphenol A modified with (poly)ethylene oxide di(meth)allyl ether, (poly)
Examples include di(meth)allyl ether of propylene oxide-modified bisphenol A, but are not limited thereto.

Also, a mixture of two or more of these may be used.

The synthesis of the mercapto group-containing polymer using polythiol and polyene is carried out by mixing and stirring the two at a temperature of 0° C. or higher, and it is also possible to use a catalyst if necessary. The molar ratio of mercapto group to carbon-carbon unsaturated double bond is 1.1 to mercapto group/double bond.
100 is preferred. Particularly preferably, it is 1.4 to 20. In addition, in this reaction as well, as in the reaction of polyepoxide and polythiol, the product is obtained in the form of a mixture in most cases, so separation and purification may be required.

As the polyene having no ester bond to be reacted with the mercapto group-containing polymer obtained as in (1) or (2) above, the polyene used in (2) is suitable.

The ratio of the mercapto group-containing polymer to the polyene used in the composition of the present invention is determined by the molar ratio of the mercapto group of the mercapto group-containing polymer to the carbon-carbon unsaturated double bond of the polyene, and the ratio is 1.5: 1 to 1:1.5, preferably 1.2:1 to 1:1°2, most preferably approximately 1:
It is 1. If the ratio of the mercapto group-containing polymer to the polyene is outside the above range, problems may occur, such as a strange odor being produced after curing, or the hardness of the cured product being too low, and in severe cases, not curing.

The photopolymerization initiators used in the present invention include benzophenone, p-methoxybenzophenone, 4゜4-bisdimethylaminobenzophenone, xanthone, thioxanthone, chlorothioxanthone, m-chloroacetone, propiophenone, anthraquinone, benzoinmethyl Examples include, but are not limited to, ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzyl, benzyl dimethyl ketal, acetone phenone, 2,2-jethoxyacetophenone, 2-hydroxy 2゜2-dimethylacetophenone, etc. It's not a thing. The amount of photopolymerization initiator used is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the mercapto group-containing polymer and polyene.

The composition of the present invention contains the above-mentioned mercapto group-containing polymer, polyene, and photopolymerization initiator as essential components, and optionally an antioxidant, a polymerization inhibitor, a plasticizer, a thixotropy imparting agent, and a silane cuff puller. Additives such as agents, chelating agents, curing accelerators, dyes, pigments, fillers, antistatic agents, and surfactants may be used within the range that does not impair the purpose of the present invention.

The thus-produced laminate in which the photocurable composition is interposed as an adhesive layer is produced by applying the present photocurable composition to one side of two plates or films, one or both of which can transmit actinic rays. After stacking the two sheets, actinic rays are irradiated from the transparent side. ■ A spacer of any thickness is sandwiched between two plates or films, one or both of which can transmit actinic rays.
It is produced by pouring the photocurable composition of the present invention and then irradiating actinic rays from the transparent side (curing and adhering). Examples of materials that can transmit actinic rays include glass, polycarbonate, polystyrene, acrylic resin, etc., but are not limited thereto. Furthermore, if actinic rays are transmitted, it is also possible to create a laminate in which three or more plates or films are stacked and a photocurable composition is interposed between them.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

Example 1 947 g of triglycol dimercaptan, 553 g of bisphenol A type epoxide,
1.2 g of 2,4.6-tris(dimethylaminomethyl)phenol was added, heated to a temperature of 150°C, and reacted for 8 hours with stirring. The concentration of mercapto groups in this product was 4.3 mmol/g.

This product and triallyl isocyanurate are mixed so that the molar ratio of mercapto group: vinyl group is 1:1,
Furthermore, 0.2 parts by weight of benzyl dimethyl ketal was added (blended viscosity 700 cps), filled into a 25φ x 5mm polyethylene cup, and placed under a 400W ultraviolet lamp for 3 hours.
Irradiation was performed for 30 minutes at a distance of 0 cm.

The obtained cured product was heated at a temperature of 70°C and a humidity of 80% for 4 hours.
When the hardness was compared with the hardness immediately after curing after being left for 0 days, no decrease in hardness was observed. These conditions and results are summarized in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that 760 g of triglycol dimercaptan and 740 g of bisphenol A epoxide were used. The conditions and results are shown in Table 1.

Example 3 The same procedure as in Example 1 was carried out except that 676 g of triglycol dimercaptan and 824 g of bisphenol A type epoxide were used. The conditions and results are shown in Table 1.

Example 4 In a 31 glass reactor, 1129 g of triglycol dimercaptan was added to Tris(2,3-epoxy).

Add 371g of propyl isocyanurate and heat to 12
The mixture was heated to 0° C. and reacted for 8 hours with stirring. Using the mercapto group-containing polymer thus obtained, a cured product was prepared in the same manner as in Example 1 and subjected to a moisture resistance test.

The conditions and results are shown in Table 1.

Example 5 Triglycol dimercaptan 1002g, tris(2,3-epoxypropyl)isocyanurate) 498g
The same procedure as in Example 4 was conducted except that g was used. The conditions and results are shown in Table 1.

Example 6 1050 g of triglycol dimercaptan and 503.4 g of triallylisocyanurate were placed in a 31 glass reaction vessel.
g was added, heated to a temperature of 60°C, and nitrogen bubbling (51/win) was performed into the liquid for 10 minutes while stirring. Then, ■, 1-bis(t-butylperoxy) 3.3
．． 5-) Limethylcyclohexane (Perhexa 3M, NOF type) was added in 3 portions of 100+qr once every 30 minutes, and after the final addition, the reaction was carried out at 70° C. for 3 hours. The concentration of mercapto groups in this product was 3.1 mmol/g.

When a cured product was prepared using this product in the same manner as in Example 1 and subjected to a moisture resistance test, no decrease in hardness was observed (immediately after curing: Shore A74, after moisture resistance test: Shore A-75).

Example 7 A silicon spacer (0.5 m thick) was sandwiched between two glass plates measuring 200 m long, 200 m wide, and 3 gm thick.
The edges of the glass were sealed with polyester tape, leaving a composition inlet. After pouring the photocurable composition used in Example 1 through the injection port and filling the gap, the injection port was sealed, and the composition was cured by irradiation for 60 minutes at an ultraviolet intensity of 3a+w/c+j, and glass lamination was performed. created a body. This laminate was heated at a temperature of 70°C and a humidity of 80%.
Although the laminate was allowed to stand for several days, no change was observed in the laminate.

Comparative Example 1 The same procedure as in Example 1 was carried out except that 135 g of triglycol dimercaptan and 1365 g of bisphenol A type epoxide were used. In this product, all mercapto groups (
I was not able to admit. The conditions and results are shown in Table 2.

Comparative Example 2 Curing and moisture resistance tests were conducted in the same manner as in Example 1, except that triglycol dimercaptan was used instead of the mercapto group-containing polymer. Although the moisture resistance test results were good, the blended viscosity was very low. The conditions and results are shown in Table 2.

Comparative Example 3 The same procedure as in Example 1 was carried out except that 1485 g of triglycol dimercaptan and 15 g of bisphenol A type epoxide were used. The mercapto group concentration of this product is 11++
It was the same as triglycol dimercaptan in wol/g, and no modification by polyepoxide was observed. The conditions and results are shown in Table 2.

Comparative Example 4 Tris-2-hydroxyethyl isocyanurate Using 1186 g of tris-β-mercaptopropionate, 314 g of bisphenol A type epoxide, and 1.2 g of 2°4.6-)lis(dimethylaminomethyl)phenol,
The same procedure as in Example 1 was carried out except that the reaction was carried out at a temperature of 80° C. for 10 hours. Although a product with a very high viscosity was obtained, the hardness was greatly reduced in the moisture resistance test. The conditions and results are shown in Table 2.

(Effects of the Invention) As described above, the photocurable composition of the present invention can have a very high viscosity, and is useful as a sealant, adhesive, or paint in areas where thickness is required. . Furthermore, since it does not undergo hydrolysis, it can be used in fields where water and moisture resistance are required.

Claims (1)

[Claims] 1. A mercapto group-containing polymer having no ester bond;
A photocurable composition consisting of a polyene that does not have an ester bond and a photopolymerization initiator. 2. Mercapto group-containing polymer without ester bonds;
A laminate comprising a material, one or both of which can transmit actinic rays, characterized in that a photocurable composition comprising a polyene having no ester bond and a photopolymerization initiator is interposed as an adhesive layer.