JPS6386714A - Resin composition and potting composition therefrom - Google Patents

Abstract

PURPOSE:To provide a resin composition useful for ultraviolet-curable potting coatings, comprising a polyurethane acrylate, bisphenol type epoxy acrylate (optional), and each specific (meth)acrylate and (meth)acrylamide. CONSTITUTION:The objective composition comprising (A) a polyurethane acrylate (pref. with an average molecular weight 1,000-2,000, polyether polyol- or polyester polyol-based one), (B), as an optional component, a bisphenol type epoxy acrylate, (C) a compound of formula I [R1 is H or CH3; R2 is of formula II (X1-X3 are each H or 1-20C alkyl) or 1-20C alkyl] (pref. a reaction product from phenyl glycidyl ether and acrylic acid), and (D) a second compound of formula III (R3 is H or CH3; R4 and R5 are each H, CnH2n+1, CmH2m+1 or CmH2m+1OCH2CH2; n and m are each 1-28) [e.g., N-methoxymethyl (meth) acrylamide].

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a resin composition and a potting composition, and is particularly useful as an ultraviolet curable potting coating.

(Conventional technology) Unlike simple thin-film coating, botting coating provides a thick coating with a convex lens feel and depth, so it has a unique image that cannot be obtained with current coating technology, and this image is unique. It can be used to manufacture interior and exterior parts of automobiles (e.g. malls,
emblems, marks, etc.), home appliances, light electrical appliances, and miscellaneous goods.

Conventionally, two-component curing polyurethane resins have been used for such botting coatings because they have excellent weather resistance, a strong coating film, and excellent durability.

(Problems to be Solved by the Invention) Two-component curing polyurethane resins have many good points as mentioned above, but they are troublesome to handle because the two components must be mixed before use. Since it uses incyanate, it has problems such as the need to be careful about ventilation etc. when using it. On the other hand, in recent years, UV-curable compositions have been widely used for reasons such as saving resources, saving energy, improving workability, and improving productivity.
For example, JP-A-49-133491゜ JP-A-57-835
Although many other polyurethane acrylate compositions such as No. 62 have been proposed, the reality is that almost no UV-curable compositions have been proposed as coatings for botting.

(Means for solving problems) The inventors aim to solve the above problem.

As a result of extensive research, we have succeeded in providing a composition for botting that has quick UV curability, the cured product is strong, and has excellent transparency. That is, 1 the present invention comprises (1) polyurethane acrylate (A) and as an optional component bisphenol-type epoxy acrylate (2 and general formula [■] crystal (in formula [I], R plate is H or C) (3), R2 has 3 atoms, and Xl, I2 and the older brother each have H or 1 to 2 carbon atoms.
0 alkyl group. ) (Ω and the general formula [■] (in the formula [■]),
R3 is H or CH3, R4 and R5 are H or C
nHzn++ or CnH2m+10CFI2 or Cm)
hm+t0CHxCI-1s, and n and m are each integers from 1 to 28. ) Compound (D
and (2) polyurethane acrylate (A, bisphenol-type epoxy acrylate (B) as an optional component, and the general formula [I
] The present invention relates to a composition for botting, characterized in that it contains a compound represented by (q) and a compound 0 and ? represented by the general formula [■].

The polyurethane acrylate (A) used in the present invention usually has an average molecular weight of 500 or more, preferably 1000 to 2
It is 000. Such polyurethane acrylates include polyurethane acrylates of polyether polyols having ether groups in one molecule, polyurethane acrylates of polyester polyols having ester groups, or polyurethane acrylates and carbonate groups having both ether groups and ester groups in the molecule. Examples include polyurethane acrylate of carbonate diol with

Examples of polyether polyols include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and 1,3-phthylene glycol.
1.4-phthylene glycol, 1.6-hexanediol, neopentyl glycol, cyclohexane dimetatool, 2゜2-bis(4-hydroxycyclohexyl)
A compound obtained by adding ethylene oxide or propylene oxide to propane, bisphenol A, etc. can be used. Polyester polyol can be obtained by reacting an alcohol component and an acid component. For example, polypropylene glycol, polyethylene f I
J: I-L, polytetramethylene glycol and 1.
3-butylene glycol, 1,4-phthylene gelicol, 1,6-hexanediol, neopentyl glycol, cyclohexane dimetatool% 2,2-bis(4-
A compound in which ethylene oxide or propylene oxide is added to (hydroxycyclohexyl) propane, bisphenol A, etc., or a compound in which nibsilone caprolactone is added is used as the alcohol component, while adipic acid, cepacic acid, azelain is used as the acid component. Acids, dibasic acids such as dodecanedicarboxylic acid and their anhydrides can be used.

A compound obtained by simultaneously reacting the above-mentioned alcohol component, acid component, and nibsilone caprolactone can also be used as the polyester polyol. or,
Examples of carbonate diols include compounds that can be produced as follows. That is, carbonate derivatives, such as diethyl carbonate, bis-chlorophenyl carbonate, dinaphthyl carbonate, phenyl-rudylucarbonate,
Phenyl-chlorophenyl-carbonate, 2-tolyl-4-tolyl-carbonate, dimethyl carbonate.

Diaryl carbonates such as diethyl carbonate or diaryl carbonate diols.

Examples, t, 1,6-hexanediol, neopentyl glycol, 1,4-butanediol, 1,8-octanediol, 1,4-bis-(hydroxymethyl)-cyclohexane, 2-methylpropanediol, A polyester which is a reaction product of propylene glycol, diptylene glycol or the above diol compounds and a dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, hexahydrophthalic acid, or a reaction product of ε-caprolactone. It can be obtained by transesterification reaction with diol etc.

It can also be produced by reacting phosgene with the diols mentioned above. The carbonate diol obtained in step 5 is a monocarbonate diol having one carbonate structure in the molecule or a polycarbonate diol having two or more carbonate structures in the molecule, and can be easily obtained from the market. For example, Desmofene 2020E (manufactured by Sumitomo Bayer ■, average molecular weight 2000
), DN-980 (manufactured by Nippon Polyurethane ■, average molecular weight 2000), DN981 (manufactured by Nippon Polyurethane @, average molecular weight 11000).

DN-982 (made from Japanese polyurethane, average molecular weight 2)
000), DN-983 (manufactured by Nippon Boliutan ■, average molecular weight 1000), and the like.

To obtain polyurethane acrylate (Aw) using these polyether polyols, polyester polyols, and carbonate diols, an organic diisocyanate and a polymerizable monomer having a hydroxyl group are added to the hydroxyl group of the polyol in a place substantially free of NCO groups. Polyurethane acrylate (substrate) can be obtained by reacting up to 4. Typical organic diincyanates include tolylene diincyanate, 4.
Aromatic diisocyanates such as 4-diphenylmethane diincyanate, inborone diincyanate, 4.4'
-Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2-trimethylhexamethylene diisocyanate, and as polymerizable monomers having a hydroxyl group, β-hydroxyethyl acrylate , β-hydroxypropyl acrylate, β-hydroxylauryl acrylate, and acrylates having a hydroxyl group such as nibsilon caprolactone-β-hydroxyethyl acrylate adduct. Although the reaction between NCO groups and OH groups proceeds without a catalyst, for example, tertiary amines such as triethylamine, organometallic compounds such as dibutyltin silaurylate and dibutyltin diacetate, or tin chlorides, etc. Any conventional catalyst may be used.

Particularly preferred polyurethane acrylate (4) is:

It is a polyurethane acrylate of polyether polyol and polyester polyol, and the organic diisocyanate includes inphorone diincyanate, 4.4'-
Particularly preferred is dicyclohexylmethane diincyanate.

The amount of polyurethane acrylate used in the composition is 20
It is preferably 60% by weight, particularly 30-50% by weight.

Bisphenol type epoxy acrylate (as a,
Epoxy acrylate made by reacting bisphenol A type epoxy resin (e.g. Shell Chemical ■, Epicor 1001, 1002, 1004, etc.) with acrylic acid, bisphenol F type epoxy resin (e.g. Shell Chemical ■)
Made.

Examples include epoxy acrylate made by reacting Epicote 807) with acrylic acid. Bisphenol type epoxy acrylate (the amount of B used is O in one composition)
~30% by weight, especially 2-10% by weight
It is preferable that A compound represented by the general formula "D" (Q is a monofunctional epoxy compound (e.g., phenyl glycidyl ether, t-butylphenol glycidyl ether, 0-cresol glycidyl ether, m
-cresol glycidyl ether, p-cresol glycidyl ether, nonylphenol glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, stearyl glycidyl ether, methyl glycidyl ether, and the like. ) and (meth)acrylic acid by a known method.

Particularly preferred are compounds obtained by reacting phenyl glycidyl ether or cresol glycidyl ether with acrylic acid.

When reacting this monofunctional epoxy compound with (meth)acrylic acid, it is preferable to use a catalyst. As the catalyst, known catalysts such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc. can be used, and the amount used is preferably 0.05 to 10% by weight based on the weight of one reaction solution, particularly It is preferable to use 0.1 to 5% of the background. (for 1 chemical equivalent of the epoxy group of the monofunctional epoxy compound)
The amount of meth)acrylic acid used is preferably 0.8 to 1.5 chemical equivalents, particularly preferably 0.9 to 1.1 chemical equivalents. The reaction temperature is preferably 60 to 150°C, especially 70°C.
~100°C is preferred. It is preferable to add a polymerization inhibitor to prevent polymerization during the reaction. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-butylphenol, α−
Examples include nitroso-β-naphthol, p-benzoquinone, naphthoquinone, phenothiazine, N-nitron phenylamine, copper salt, and the like. The amount used is usually 0.01 to 1% by weight per reaction mixture.

Compound represented by the general formula [■] (The amount of Q used is.

It is preferably 15 to 45% by weight in the composition, especially 20% by weight.
Preferably it is 40% by weight. - Specific examples of the compound (g) represented by the general formula [■] include N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methyl ( meth) acrylamide, N,
N-dimethyl(meth)acrylamide, N-alkyl(
Examples include acrylamide (having 6 to 28 carbon atoms). The usage amount of the compound represented by the general formula [■] is preferably 3 to 20% by weight, particularly 5 to 20% by weight, in one composition.
Preferably it is 10% by weight. The resin composition of the present invention (
The botting composition) can be cured by a known method. For example, it can be cured by ultraviolet light. In the case of curing with ultraviolet light, it is necessary to use a photoinitiator.

Any known photopolymerization initiator may be used, but it is required to have good storage stability after blending.

Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin propyl ether. acetophenone series, 2-hydroxy-2-methylpropiophenone, 4-impropyl-2-hydroxy-2-methylpropiophenone, 4'-dodecyl 2-hydroxy-
Propiophenone series such as 2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and 2-ethylanthraquinone%
Anthraquinones such as 2-chloroanthraquinone,
Other examples include thioxanthone-based photopolymerization initiators. Especially preferred ones.

]-Hydroxycyclohexylphenylketone.

Examples include benzyl dimethyl ketal. These photopolymerization initiators may be used alone or in a mixture of two or more in any proportion. The amount used is usually 0 to 1 per composition.
10% by weight is preferred, particularly 1 to 5% by weight.

The resin composition (potting composition) of the present invention may optionally contain components (Al, fB), (C
) and acrylic esters and various additives other than [F] may be added, and acrylic esters include carpitol acrylate, phenoxyethyl acrylate,
Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate (manufactured by Nippon Kayaku ■,
KAYARADHX-220, KAYARADA HX
-620), diacrylate of ethylene oxide adduct of bisphenol A (manufactured by Nippon Kayaku ■, KAYARAD
R-551) and the like. The amount of acrylic ester used in the composition is preferably 0 to 20% by weight, particularly preferably 0 to 15% by weight. Further, examples of the additives include polymerization inhibitors, antioxidants, surfactants, and the like.

The resin composition of the present invention is useful for potting, and can also be used as a coating agent for glass, a gR fiber treatment agent, etc.

When potting coating is performed using the botting composition of the present invention, a suitable coating method is to pass metered pulp through a pump.

When coating the composition for botting 1 The thickness of the coating film obtained by the coating method of the present invention is not particularly limited, but is usually 0.5 to
About 5If11 is preferable.

The botting composition of the present invention is easily cured by ultraviolet irradiation. Curing of the botting composition of the present invention by irradiation with ultraviolet rays can be carried out by a conventional method. For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp, a xenon lamp, or the like.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
Parts in the examples are 1 part by weight.

[Synthesis example of polyurethane acrylate (2)] Synthesis example 1
゜ Equipped with a stirrer, temperature control device, thermometer, and condenser 1! l
In a lt reactor, 336 parts of polyester diol (a polyester diol with a molecular weight of 480 consisting of neopentyl glycol and adipic acid) and 3 parts of inphorone diisocyanate were added.
11.2 parts of 2-hydroxyethyl acrylate, 0.4 parts of methoquinone, and dilauric acid were added. -0.15 part of butyltin was charged, and after raising the temperature, the reaction was carried out at 75 to 80°C. The reaction was continued until completion as indicated by less than about 0.1% free incyanate groups. The product has the following properties.

Viscosity 1840 poise (60°C) Synthesis Example 2 In the same reactor as Synthesis Example], polyester diol (molecular weight 480 consisting of neopentyl glycol and adipic acid) was added.
230 parts of polyester diol), 230 parts of polytetramethylene glycol (manufactured by Odugaya Chemical Co., Ltd., PTG-500P)
, molecular weight approximately 2000') and 200 parts of inphorone diisocyanate, and the temperature was raised to 75°C.
Reacted for 0 hours.

The reaction solution was then cooled to 60°C, and 68.7 parts of 2-hydroxyethyl acrylate - 0.37 parts of methquinone,
Add 0.14 parts of di-n-butyltin dilaurate,
The reaction was carried out at an elevated temperature of 75-80°C.

The reaction was continued until completion as indicated by less than about 0.1% free incyanate groups. The product has the following properties.

Viscosity 15] Opoise (60°C) Synthesis Example 3゜In the same reactor as Synthesis Example 1, 9.3 parts of ethylene glycol, 68 parts of polyester diol (a polyester diol with a molecular weight of 480 consisting of neopentyl glycol and adipic acid), 222.3 copies? After charging and raising the temperature, the mixture was reacted at 75°C for 10 hours, then the reaction solution was cooled to 60°C, and 117.9 parts of 2-hydroxyethyl acrylate and 0.26 parts of methoquinone were added.
After raising the temperature, the reaction was carried out at 75-80°C. The reaction was continued until completion as indicated by less than about 0.1% free incyanate groups. The product has the following properties.

Viscosity 465 poise (60°C) [Bisphenol type epoxy acrylate (synthesis example of a)] Epoxy resin (manufactured by Shell Kagaku ■, Epicoat 1004,
Epoxy half amount 924.6) 240 parts, acrylic acid 17.
3 parts, 0.2 parts of methoquinone and 2 parts of triphenylstibine.
．． 0 parts, acrylic ester of phenylglycidyl ether (manufactured by Nippon Kakei@, KAYARAD) as a diluent.
After charging 189 parts of R-128') and raising the temperature, the reaction was continued at 90°C until the acid value (■KOH/g) became 1 or less. The product has the following properties.

Viscosity: 484 poise (60°C) [Synthesis example of compound (O) represented by general formula 0] Synthesis example 5゜Into the same reactor as Synthesis example 1, 152.5 parts of phenyl glycidyl ether (epoxy equivalent: 152.5) , 68.5 parts of acrylic acid, 2.2 parts of triphenylstibine, and 0.1 part of methoquinone were added, and the temperature of the mixed solution was 90 to 95°C.
The reaction was carried out until the acid value (rr@KOH/g) became 1 or less while maintaining the following properties.

Viscosity 225 cps (25°C) Synthesis Example 6
, By the same operation as in Synthesis Example 5, p-cresol glycidyl ether (epoxy equivalent: 165.7) 331. 1 part of acrylic acid, 2.3 parts of triphenylstibine, and 0.23 part of methoquinone were reacted to obtain a liquid product. The product has the following properties.

Viscosity 85 cps (25°C) [Example of resin composition (botting composition)] 45 parts of polyurethane acrylate (4) obtained in Example 1゜Synthesis example], bisphenol type obtained in Synthesis example 4 Epoxy acrylate (B10 parts, compound obtained in Synthesis Example 5 (035 parts, N-
110 parts of butoxymethyl acrylamide, and -hydroxycyclohexylphenyl ketone (Ciba)
Manufactured by Gaiki ■, Irgacure 184, photopolymerization initiator)
Resin composition (botting composition) A was prepared by mixing 5 parts of methquinone and 0.1 part of methoquinone. Characteristics of cured product? : Shown in Table 1.

Example 2゜Polyurethane acrylate obtained in Synthesis Example 2) (A135 parts, bisphenol type epoxy acrylate fB obtained in Synthesis Example 4) 10 parts 1 Compound obtained in Synthesis Example 5 (030 parts, N
-butoxymethylacrylamide ■) 10 parts, 2 moles of neopentyl glycol hydroxypivalate ε-caprolactone attached W diacrylate (manufactured by Nippon Kayaku ■, K
AYARAD ) (X-620) 15 parts and ]-hydroxycyclo, xylphenyl ketone 5 parts, methoquinone O
Mix part N and prepare resin composition (potting composition) B.
Prepared for ¥. Table 1 shows the properties of the cured product.

Example 3 30 parts of polyurethane acrylate (substrate) obtained in Synthesis Example 1, bisphenol type epoxy acrylate obtained in Synthesis Example 4
)fB) 10 parts 1 Compound obtained in Synthesis Example 6 (030 parts, carpitol acrylate 15 parts, N.

A resin composition (botting composition) C was prepared by mixing 5 parts of N-dimethylacrylamide (DJ, 5 parts of 1-hydroxycyclohexylphenyl ketone, and 0.1 part of methoquinone). It is shown in Table 1.

Example 4゜35 parts of polyurethane acrylate (2) obtained in Synthesis Example 3, 10 parts of bisphenol-type epoxy acrylate fB obtained in Synthesis Example 4 1 Compound obtained in Synthesis Example 6 (030 parts,
10 parts of N-ethoxyethyl acrylamide (up to), 15 parts of phenoxyethyl acrylate, 5 parts of 1-hydroxycyclohexylphenyl ketone, and 0.1 part of methquinone were mixed to prepare resin composition (botting composition) D. did. Table 1 shows the properties of the cured product.

Example 5 45 parts of polyurethane acrylate (2) obtained in Synthesis Example 2 1 25 parts of the compound obtained in Synthesis Example 5, 5 parts of N-butoxymethylacrylamide (B), 25 parts of phenyloxyethyl acrylate and 1-hydroxy Resin composition (botting composition) E was prepared by mixing 5 parts of cyclohexyl phenyl ketone and 0.1 part of methoquinone.Characteristics of the cured product are shown in Table 7.

Curing properties (mJ/cm2) in Table 1 above: The compositions A, B, C, D and E were painted on a glass plate (thickness 211111)
L, UV irradiation amount (mJ/cm2) until the surface and interior are sufficiently cured when irradiated at a position 8 cm below the light source placed parallel to a high-pressure mercury lamp (lamp output 2 KW) Transparency 2 Curing properties listed above Evaluation was made using Test Piece 7 on which .

○...Transparent △...Slightly opaque ×...opaque bendability 2.Evaluation was made using the test piece whose curing properties were measured as described above.

C)...From the front and back] No cracking even after 80 folds.

△...No cracking even when folded 180 degrees from the front.

If you bend it 180 degrees from the back, it will crack.

×...It cracks when folded 180 degrees from the front and back sides.

Toughness: Evaluated using the test piece whose hardenability was measured above.

C)... Even if you scratch the surface with a knife and bend it, the scratch will not spread.

△・・・・・・When you scratch the surface with a knife and bend it, the scratch spreads a little.

×...If you scratch the surface with a knife and bend it, the scratches will spread easily.

(Effects of the Invention) The resin composition of the present invention has a fast curing speed, can be cured into a thick film, the cured film is transparent, and has excellent bendability and toughness, and is particularly suitable for a coating for botting.

Claims (2)

[Claims] (1) Polyurethane acrylate (A) and bisphenol-type epoxy acrylate (B) as an optional component, general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In formula [I], R_1 is H or CH_3 And R_
2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or carbon number 1 ~
20 alkyl groups, and X_1, X_2 and X_3 each represent H or an alkyl group having 1 to 20 carbon atoms. ) Compound (C) represented by the general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula [II], R_3 is H or CH_3, and R_4
and R_5 is H or CnH_2_n_+_1 or CmH
_2_m_+_1OCH_2 or CmH_2_m_+_
1OCHCH_2, where n and m are each 1 to 28
is an integer. ) A resin composition comprising a compound (D) represented by: (2) Polyurethane acrylate (A), bisphenol-type epoxy acrylate (B) as an optional component, and a compound (C) represented by the general formula [I] ▲ Mathematical formula, chemical formula,
There are tables, etc. ▼ [I] (In the formula [I], R_1 is H or CH_3, R_
2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or carbon number 1 ~
20 alkyl groups, and X_1, X_2 and X_3 each represent H or an alkyl group having 1 to 20 carbon atoms. ) and general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In formula [II], R_3 is H or CH_3, and R_4
and R_5 is H or CnH_2_n_+_1 or CmH
_2_m_+_1OCH_2 or CmH_2_m_+_
1OCH_2CH_2, where n and m are each from 1 to
It is an integer of 28. ) A potting composition comprising a compound (D) represented by: