JPH06234823A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in dry characteristics in air, adhesion, water resistance and tonghness and useful as a molded article of FRP, etc., by dissolving a specific polyether urethane acrylate resin in a polymerizable unsaturated monomer. CONSTITUTION:The composition is obtained by compounding (A) a polyether- urethane acrylate resin having both of a (meth)acryloyl group and an allyl ether group and (B) a polymerizable unsaturated monomer (as a general example a styrene monomeric compound, e.g. styrene). The component A is preferably obtained by reacting polyisocyanate with polyether polyol at a ratio NCO/OH of 2-1.5 to obtain a NCO containing compound and reacting the NCO containing compound with an acrylic compound containing OH group and an allyl ether compound containing OH group. As an acrylic compound containing OH group, 2-hydroxyethyl (meth)acrylate, etc., and as an allyl ether compound containing OH group, ethylene glycol monoallyl ether, etc., are respectively preferable.

Description

Detailed Description of the Invention

The present invention relates to a resin composition, and more particularly to a (meth) acryloyl group- and allyl ether group-containing polyether urethane resin composition having air-drying properties and excellent in water resistance and toughness.

[0002]

BACKGROUND OF THE INVENTION (Meth) acryloyl group-containing polyetherurethane resin has the characteristic that it is water-resistant but highly flexible, which is not present in unsaturated polyester resins.
Due to its anaerobic property, it has a drawback that the surface is sticky. This drawback is a serious problem in practical use when it is used as a laminated product or a covering material. For example, use this resin to impregnate fiber reinforcement
When cured to form FRP, the surface is significantly deteriorated and dirty,
Further, when used as a gel coat, the surface is not sufficiently hardened, so that when the glass mat is laminated and boiled, there is a problem that the gel coat layer and the FRP layer are separated from each other.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to improve the air-drying property of a (meth) acryloyl group-containing polyether urethane resin at the time of curing, and to improve the secondary adhesive property, water resistance and the like.

[0004]

The present invention provides a polyether urethane resin having a (meth) acryloyl group and an allyl ether group, and in particular, the resin is obtained by adding an excessive amount of polyisocyanate to a polyether polyol. The present invention relates to a resin composition containing a urethane resin obtained by reacting an isocyanate group-containing compound with a hydroxyl group-containing allyl ether compound and a hydroxyl group-containing acrylic compound, and a polymerizable unsaturated monomer.

[0005]

[Structure] A polyether urethane resin having a (meth) acryloyl group and an allyl ether group of the present invention (hereinafter referred to as an allyl ether group-containing polyether urethane acrylate) has at least one (meth) acryloyl group in a molecule. And having at least one allyl ether group. Such a resin is obtained, for example, by reacting a polyisocyanate with a polyether polyol, a hydroxyl group-containing acrylic compound, and a hydroxyl group-containing allyl ether compound, and the equivalent ratios of the isocyanate group and the hydroxyl group are approximately the same. A compound obtained by reacting a compound, specifically, first reacting a polyether polyol and a polyisocyanate to obtain an isocyanate group-containing compound, and then reacting it with a hydroxyl group-containing acrylic compound and a hydroxyl group-containing allyl ether compound preferable.

The term "polyether polyol" as used herein means
The number average molecular weight is preferably 400 or more, particularly 500 to 30.
No. 00, and examples thereof include polyoxypropylene diol, polytetramethylene glycol, and polyoxymethylene diol.

Examples of polyisocyanates include 2,4-tolylene diisocyanate and its isomers or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate,
Hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane tritosocyanate, Vernock D-750, Crisbon NX
(Products of Dainippon Ink and Chemicals, Inc.), Desmodur L (Product of Sumitomo Bayer Co., Ltd.), Coronate L (Product of Nippon Polyurethane Co., Ltd.), Nukenate D102 (Product of Takeda Pharmaceutical Co., Ltd.), etc., either alone or Two or more types can be used. Of the above polyisocyanates, diisocyanates, especially TDI are preferably used.

The hydroxyl group-containing acrylic compound is preferably a hydroxyl group-containing (meth) acrylic acid ester, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate; polyethylene. Alcohol mono (meth) acrylates having two hydroxyl groups such as glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri ( Partial (meth) acrylates of alcohols having three or more hydroxyl groups such as (meth) acrylate and the like can be mentioned.

As the hydroxyl group-containing allyl ether compound, known and conventional ones can be used. Among them, typical ones are ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether and polyethylene glycol monoallyl. Ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1.2-butylene glycol monoallyl ether, 1.3-butylene glycol monoallyl ether, hexylene Glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glycerin diali Ethers, include allyl ether compound of a polyhydric alcohol such as pentaerythritol triallyl ether, allyl ether compound having one hydroxyl group are preferred.

An example of the method for producing the allyl ether group-containing polyether urethane acrylate of the present invention is as follows:
First, the polyisocyanate and the polyether polyol are preferably NCO / OH so that the number average molecular weight thereof is 800 to 50,000, and particularly preferably 1,000 to 20,000.
= 2 to 1.5 to produce a terminal isocyanate group-containing compound, and then a hydroxyl group-containing acrylic compound and a hydroxyl group-containing allyl ether compound are reacted so that the hydroxyl groups are approximately equivalent to the isocyanate groups. The hydroxyl group-containing acrylic compound / hydroxyl group-containing allyl ether compound in this case preferably has a molar ratio of 90/10 to 2
It is 0/80, more preferably 70/30 to 40/60. Alternatively, first, a hydroxyl group-containing acrylic compound and a hydroxyl group-containing allyl ether compound are reacted with polyisocyanate, and then the obtained isocyanate group-containing compound is reacted with a polyether polyol, preferably a number average molecular weight of 800 to 50,000, more preferably 1000
Up to 20,000 allyl ether group-containing polyether urethane acrylates can be produced.

The obtained allyl ether group-containing polyether urethane acrylate is dissolved in the polymerizable unsaturated monomer. Examples of the polymerizable unsaturated monomer include styrene,
Vinyltoluene, methylstyrene, paramethylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl, ketone methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile,
Vinyl compounds such as glycidyl methacrylate and diallyl phthalate, diallyl fumarate, diallyl succinate, allyl compounds such as triallyl cyanurate, etc. The styrenic monomers are generally used.

The resin composition of the present invention is preferably a resin composition in which 90 to 20 parts by weight of an allyl ether group-containing polyether urethane acrylate and 10 to 80 parts by weight of a polymerizable unsaturated monomer are mutually dissolved.

A polymerization inhibitor is preferably added to the resin composition of the present invention, and as the polymerization inhibitor, trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert- Butyl catechol, 2,6-tert-butyl-4-methylphenol and the like can be mentioned. The amount used is preferably 40 to 1000 ppm in the resin composition.

The resin composition of the present invention is usually cured by adding a curing agent. Examples of the curing agent that can be added include one or more selected from ultraviolet curing agents, electron beam curing agents, photocuring agents, and heat curing agents. The amount of the curing agent used is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin composition.

The ultraviolet curing agent is a photosensitizing substance,
Specific examples thereof include benzoin ether type compounds such as benzoin alkyl ether, benzophenone type compounds such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-
Acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone , 2-isopropyl thioxanthone and other thioxanthone compounds.

Examples of electron beam curing agents include halogenated alkylbenzenes and disulfide compounds.

Examples of the photo-curing agent include hydroxyalkylphenone compounds, alkylthioxanthone compounds, and sulfonium salt compounds.

Examples of the thermosetting agent include organic peroxides,
Specifically, known materials such as diacyl peroxide type, peroxy ester type, hydroperoxide type, dialkyl peroxide type, ketone peroxide type, peroxyketal type, alkyl perester type, percarbonate type are used. , Kneading conditions, curing temperature, etc.

Further, an organic metal salt such as cobalt naphthenate or cobalt octenoate can be used as a curing accelerator in the composition of the present invention.

The composition of the present invention includes unsaturated polyester resin, vinyl urethane resin, vinyl ester urethane resin, polyisocyanate, polyepoxide, acrylic resins, alkyd resins, urea resins, melanin resins, polyvinyl acetate, Vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers and nitrocellulose, cellulose derivatives such as cellulose acetate butyrate and linseed oil, tung oil, soybean oil, castor oil, epoxidized oil and other oils and fats Other conventional natural and synthetic polymeric compounds such as can be added.

Further, the composition of the present invention contains glass fiber, carbon fiber, organic fiber, metal fiber or the like as a reinforcing agent in an amount of 10 to 70.
A molded product can be obtained by adding the composition in an amount of% by weight. Putty and sealing agent prepared by compounding the composition of the present invention with a filler such as calcium carbonate, talc, mica, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand. Or as a coating material. It is also effective as a material for impregnating and reinforcing cloth and kraft paper. Furthermore, other additives such as zinc stearate, titanium white, zinc white, and other various pigment stabilizers and flame retardants can be added.

The resin composition of the present invention is used as a fiber reinforced molded product (FRP), putty, cast product or coating application such as gel coating lining material.

[0023]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, "parts" in the text means parts by weight.

(Example 1) 382 parts of Mitsui polyol diol 700 (manufactured by Mitsui Toatsu Co., Ltd.) were charged into a 1-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 190 parts of TDI was added and the reaction was carried out at 80 ° C. for 5 hours while suppressing heat generation. Since the NCO equivalent was 524, which was almost the same as the theoretical value and became stable, it was cooled to 40 ° C., 119 parts of pentaerythritol triallyl ether (Daiso Co., Neoallyl P-30) was added, and 78 parts of 2-hydroxyethyl methacrylate were added, and an air atmosphere was added. The mixture was reacted at 90 ° C for 7 hours. Since the NCO% became 0.1% by weight or less, 0.067 parts of hydroquinone, 0.033 part of tertiary butyl catechol and 3 parts of styrene monomer were added.
30 parts non-volatile content 70% by weight, Gardner viscosity U,
A urethane acrylate resin composition containing an allyl ether group of Gardner Color 1 was obtained.

(Example 2) 418 parts of Mitsui polyol diol 700 were charged in the same reactor as in Example 1,
Next, add 209 parts of TDI and pay attention to heat generation at 80 ° C.
I held it for 5 hours. Since the NCO equivalent was 522, which was almost the same as the theoretical value and became stable, it was cooled to 40 ° C., and 61 parts of ethylene glycol monoallyl glycol (Waidinol AEX manufactured by Yokkaichi Gosei Co., Ltd.) and 86 parts of 2-hydroxyethyl methacrylate were added under an air atmosphere to obtain 90. The reaction was carried out at ℃ for 7 hours. Since the NCO% became 0.1% by weight or less, 0.085 parts of hydroquinone and 0.04 part of tertiary butyl catechol were added, 332 parts of styrene monomer was added, and 70% by weight of nonvolatile content and Gardner viscosity S-T A Gardner color 1 allyl ether group-containing urethane acrylate resin composition was obtained.

(Comparative Example 1) In Example 1, an acrylic urethane was synthesized without adding pentaerythritol triallyl ether.

283 parts of Mitsui polyol diol 700 (manufactured by Mitsui Toatsu) and 144 parts of TDI were charged, and the reaction temperature was kept at 80 ° C. in a nitrogen atmosphere, and after 5 hours, the theoretical NCO equivalent 516 was confirmed. The mixture was cooled to 30 ° C., charged with 109 parts of 2-hydroxyethyl methacrylate and reacted at 80 ° C. for 4 hours in a nitrogen atmosphere. Since NCO% became 0.1% by weight or less, 0.08 part of hydroquinone, tartary Butyl catechol 0.026 parts was added and styrene monomer 230 parts was added. A urethane acrylate resin composition having a nonvolatile content of 70% by weight, a Gardner viscosity R and a Gardner color 1 was obtained.

The evaluation of the above synthetic resins is shown in Table 1. [Tackiness of surface] To 100 parts of resin, 0.2 part of cobalt naphthenate (containing 6% by weight of metal) was added and stirred for about 1 minute, and 2 parts of methyl ethyl ketone peroxide was added. After stirring, the glass plate was thickened at 25 ° C. The thickness was 3 mm. After gelation, the product was placed in an oven at 50 ° C. and 30 minutes later, the surface tackiness was examined.

[Adhesiveness (after boiling)] Glass fiber (450
No.) Three sheets were laminated to form a laminated plate. After leaving for 24 hours 6
After-curing for 2 hours at 0 ℃, laminate 5cm x 5
The pieces were cut into cm and subjected to boiling at 100 ° C. for 100 hours to examine the boiling adhesiveness.

[0030]

[Table 1]

As can be seen from the above table, the resin composition of the present invention has excellent surface dryness and adhesiveness.

[0032]

EFFECTS OF THE INVENTION The resin composition of the present invention has excellent air-drying property and adhesiveness, and is excellent as FRP and coating resin.

Claims (3)

[Claims] 1. A resin composition comprising a polyether urethane acrylate resin having a (meth) acryloyl group and an allyl ether group and a polymerizable unsaturated monomer. 2. A polyether urethane resin having a (meth) acryloyl group and an allyl ether group is obtained by reacting a polyether polyol with polyisocyanate to obtain an isocyanate group-containing compound, which is then combined with a hydroxyl group-containing acrylic compound and a hydroxyl group-containing allyl group. The resin composition according to claim 1, which is obtained by reacting an ether compound. 3. A polyether urethane acrylate resin 9 having a (meth) acryloyl group and an allyl ether group.
A resin composition comprising 0 to 20 parts by weight and 10 to 80 parts by weight of a polymerizable unsaturated monomer.