JPS58136672A - Photo-curing adhesive composition for polycarbonate molding - Google Patents

Abstract

PURPOSE:To provide the titled compsn. consisting of a resin obtained by reacting a diisocyanate compd. and then an active hydrogen-contg. acrylic monomer with a specified polyol, a specified acrylic monomer, a specified satd. carboxylic acid and a photo-polymerization initiator. CONSTITUTION:The titled compsn. is prepared from (A) 10-80wt% resin obtained by reacting a diisocyanate compd. with linear polyester-polyol or linear polyether-polyol to introduce isocyanate groups at both terminals of the polymer and then reacting an active hydrogen-contg. acrylic monomer with the polymer, (B) 5-70wt% hydroxyalkyl group-contg. acrylic monomer, (C) 3-30wt% ethylenically unsatd. carboxylic acid and (D) 0.1-10wt% photopolymerization initiator. The adhesive compsn. exhibits bonding strength sufficient for partical use without imparing transparency of polycarbonate molding.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesives used in manufacturing polycarbonate-based laminates.

It is useful as a laminate made of polycarbonate, such as polycarbonate/glass, polycarbonate/polyacrylic ester*tt safety glass, windproof glass, and bulletproof glass.

Various adhesives are known as adhesives for laminated products, but polycarbonate has a strong tendency to devitrify when it comes into contact with many organic compounds, which impairs the transparency of the laminated products and does not provide sufficient adhesion. Development of strong adhesive KFi
However, the present inventor has conducted intensive research to obtain an adhesive that does not reduce the transparency of polycarbonate and can exhibit sufficient adhesive strength for practical use. Obtained by reacting a linear polyester polyol or a linear polyether polyol with a divalent iso-cyanate compound, introducing isocyanate groups into both terminal ends of the polymer, and further reacting with an active hydrogen-containing acrylic monomer. It was discovered that the object could be achieved with a composition consisting of a hydroxyalkyl group-containing acrylic monomer (S), an ethylenically unsaturated carboxylic acid (4), and a photopolymerization initiator, and accomplished the present invention. .

In component (1) of *q4, first, linear polyester polyol is a reaction product of dicarboxylic acid and diol and is linear. A 9-polyester polyol obtained using a carboxylic acid or polyol with a 5- or higher capacity is unsuitable for the KFi of the present invention because it forms a dense network structure, is hard and rough 5w1ii, and has low adhesive strength.

Examples of dicarboxylic acid #1 include aliphatic dibasic acids such as succinic acid, adivicic acid, azelaic acid, and sepacic acid, phthalic acid, tetrahydro-7thalic acid, hequinahydrophthalic acid, etc. - Nito I, “CFi,”
Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexidenediol, neopentyl glycol natol, among others, adipine glycol as a dicarboxylic acid. A combination of 1,4-butanediol and ethylene glycol is suitable as the diol.

The appropriate molecular weight is 500 to 25,001 degrees, and the number 11 is based on the type of dicarbonate, diol, and hydroxyl value (
The hydroxyl value Fi is approximately in the range of 112 to 22 (KOH*/l).

Furthermore, linear polyether glyol is a polymer obtained by addition-reacting alkylene oxide to various dihydric alcohols as described above.

Key note (4) When reacting linear polyester polyol or linear polyether polyol KQI) divalent isocyanate compound, the ratio of + and -) is +/@-1 = 1
4 to 81, in other words, the hydroxyl group of (4) and @
The ratio of the number of O incyanene groups is 1 to 20. Although it is essential that the incyanate group Fi is introduced at the end of the component, it can also be present in the chain of the component as a chain extender for the K(A) component.

(2) Two incyanate compounds include compounds having two incyanate groups in one molecule, specifically 24-) lylene diisocyanate, 2.6-) lylene diisocyanate, and Xylylene diisocyanate, P-xylylene diisocyanate, diphenylmethane 4,41 diisocyanate, hequinamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, these diisocyanates, and water-temperatured diisocyanate (1 kg), which may be used alone or in combination
It is used in more than one species.

Next, when reacting #I linear polyester polyol or linear polyether polyol with (B) divalent isocyanate compound Kc) active hydrogen-containing acrylic monomer, the molar ratio is (4 ) Polyester polyol or polyether polyol / 俤 ] Divalent isocyanate compound / (C) Active hydrogen-containing acrylic monomer with 1 to
10/2 to 11/2 is preferable.

(C') As the M hydrogen-containing acrylic monomer, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
2-droxypropyl methacrylate, N-vinylpyrrolidone, 2-hydroxyethyl acryloyl phosphate, acrylamide, methacrylamide, K-methylol acrylamide, di-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, Ethylene glycol heptanoacrylate, dipropylene glycol heptanoacrylate),)
J,N-dimethylaminoethyl acrylate and the like are used alone or in combination of two or more Fi.

2), (2), There is no specific preparation in the method for the reaction KII, and it is necessary to mix #1 (6) and (2) and heat with stirring (SO ~ 150℃ 11 degrees) When the residual incyanate base content is 1 to 15% by weight per 1 liter, add the first and further Km
f/h (approximately 40 to 55°C) and stop the reaction when the content of residual incyanate groups is 0 to 5% by weight.
/-ho - Kyoto stirrup base value of fat is preferably 1 to 1011 degrees.

During the reaction, there is no difference in the use of any S agent in combination with a polymerization inhibitor of #f and 0 weight.

Next, as the hydroxyalkyl group-containing acrylic monomer which is component (1) of this J1m light, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Examples include 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and the like.

In addition, as the ethylenically unsaturated carboxylic acid-1 which is the key ingredient of the present invention, acrylic acid and 4IIl methacrylic acid are preferably used, but other carboxylic acids such as maleic acid and crotonic acid can also be used. 〇The photopolymerization initiator which is 141 ingredients in Thu JlijlK is Teha, henzin, benzoin methyl ether, penzoin isoglobyl ether, penzoin-methyl ether, benzoin phenyl ether, acitraquinone, naphthoquinone, benzophenone, biparoin ethyl ether , pensoil peroxide, benzyl ketal,
1.1-dichloroacetophenone, para-(-gutyldichloroayatophenone, 2-chlorothioquinanthone, 2
+2- Jetoxyaceto7enone, Mitozuzketone, 1-Hydroxycyclohexylphenylketone, 2.
2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dipenzosparone, benzophenone amine A (N-
methyljetanolamine, triethylamine, etc.).

The mixing ratio Fi of each component is 10 to 8.
0% by weight, preferably 11,150 to 70% by weight.

If it is more than 10% by weight, the Shako cross-reaction will be difficult, while if it is more than 80% by weight, the viscosity of the branched solution will be high and the coating properties will be poor, which will be a practical problem.

(Ingredient #'i 5-70% by weight, preferably tilo-5
It is 0% by weight. Below 5% by weight, the solution viscosity is high;
If the amount is 0% by weight or more, the curing speed becomes too fast to be controlled, which becomes a noticeable drawback.

(Composition 1j 5 to 50% by weight, preferably FiS to 20% by weight. If it is less than 6% by weight, the adhesive strength decreases,
At 0% by weight or more, it has boat-racing properties that devitrify the polycarbonate.

The amount of component (4) to be blended is suitably selected from the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Appropriate auxiliaries and additives are used in combination with the adhesive of the present invention depending on various purposes. For example, fillers such as pigments, dyes and fillers, and auxiliary agents such as solvents and polymerization inhibitors are used. Also, depending on the type of object to be bonded, it is possible to mix other polymerizable monomers in addition to component (!1). For example, when manufacturing a laminate of polycarbonate and polyacrylic acid ester, methacrylic Approximately 5 to 20% by weight of acrylic acid or methacrylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, methyl acrylate, and glycol diacrylate [(1), (ri, (3), (4
) can exhibit stronger adhesive force.

The adhesive of the present invention is used in the production of laminates made of polycarbonate molded products, and can exhibit strong adhesive strength without impairing the transparency of the polycarbonate.

When manufacturing laminate products, the objects are polycarbonate, screws, and other materials9.

Of course, bonding of 7 is also possible. For example, polyacrylic acid ester, polymethacrylic ester, polyvinyl chloride, polyester, nylon, polyethylene, polypropylene, polyaceter I, molded products such as polystyrene and other plastic films, sheets, plates, etc. 1Kt-J glass, wood, paper, Can be bonded to metal plates, etc. and polycarbonate.
It is 1.

To manufacture a laminate product, the adhesive of the present invention is used as a base material, and the adhesive is cast or coated in an appropriate amount depending on the purpose, and then they are stacked together and irradiated with light using a high-pressure mercury lamp, UV fluorescent lamp, medium-pressure high-output mercury lamp, etc. do.

First, an organic peroxide catalyst and its accelerator are used as a curing agent.
FMI L, a method of curing by light irradiation and heating, is suitable for curing thick molded products and cases where K<-- at the time of light irradiation, so the hardening layer is preferable.

The laminated product thus obtained is often used as safety glass, etc., but depending on the type of base material to be laminated, it can also be used for the application of koji.

Next, this invention will be specifically explained with reference to examples.

The expressions ``1st grade'' or ``%'' are based on weight without any particular indication.

Example 1 1! ) Preparation of acid content resin 2/'II flask contains 1.0 mol of adipic acid, 0.56 mol of ethylene glycol, and 0 mol of 1,4-butanediol.
．． Add 56 mol of mol.
7 o'clock - Heating, stopping the reaction when the acid value reached 0.6' KOH*/P), cooling, and at 9 o'clock the hydroxyl value Fi55.6
n q, n). The number average molecular weight of this polyester polyol was Fi2080 (measured using a high performance liquid chromatograph/GPC packed column).

Next, this polyester polyol 2 mol KfiL 20%
5 mol of a mixture of 2.6-tolylene diisocyanate and aO*2.4-tolylene diisocyanate was added and stirred at a temperature of 60 to 90'C until the remaining incyanate groups were 1
．． 2-hydroxyethyl acrylate at 8%)
2.06 moles of water, 0.04510 moles of seven methyl ether hydroquinone. The mixture was stirred in the dark for 11 hours, and the reaction was stopped when 0.2% of the incyanate group remained. (Water-based value t15.5).

A transparent adhesive composition was obtained by stirring the mixture at 40°C.

This adhesive was applied on a polycarbonate plate at a rate of 10 f/W, and then a transparent polyacrylic and methyl J strip plate was superimposed, the air was expelled, and the excess adhesive was removed.

Next, with the transparent polyacrylic methyl ester facing upward, a high-pressure mercury lamp (801/cm) was applied from above for 2 seconds at a height of 10 mm.
! Irradiated.

The shear adhesive strength of the obtained laminate was measured one day later (
Crosshead speed 2 wan/+min) and 9 to 6
0 wisdom and 9. Furthermore, there was no indication that the transparency of the laminate was reduced at all.

Examples 2 to 6 [Resins of component (1) as shown in Table 1 were produced. Using it, prepare the adhesive shown in No. 23-'I1. Example IK
A laminate was produced early on.

The results are shown in @2mugi.

1st Table Abbreviation EG: Ethylene glycol 1.4-BG: +, 4-butanediol PG
:Propylene glycol DEG Nidiethylene glycol AdA:
Adipic acid SeA −: sebacic acid

Claims (1)

[Claims] 1. (1) A divalent isocyanate compound is reacted with an l-shaped polyester polyol or a linear polyether polyol to introduce isocyanate groups at both ends of the polymer,
A resin obtained by further reacting an active hydrogen-containing acrylic monomer (a polycarbonate consisting of a tetrahydroxyalkyl group-containing acrylic monomer 1 (an ethylenically unsaturated carboxylic acid, -) and a photopolymerized starting polymer) ml! Light curing for things! ! 11I-Akebono composition. 1 11) The proportion of the classification is 10-80% by weight, (the proportion of l component is 5-70% by weight, the proportion of iml I!E is 5-80% by weight)
112. The composition according to claim 111, wherein the proportion of component (4) is 0.1 to 10% by weight.