JPH1017640A - Two-package curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solventless composition having low viscosity and excellent flow, giving a cured coating film excellent in heat resistance, weather resistance, acid resistance, water resistance and elongation and being capable of thick coating. SOLUTION: This composition comprises a copolymer comprising at least 5wt.% at least one (meth)acrylate having at least one hydroxyl group and at most 95wt.% at least one ethylenically unsaturated monomer other than the (meth)acrylate and having a number-average molecular weight of 1,000-20,000 and an organic polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a two-part curable composition comprising a copolymer having a hydroxyl group and an organic polyisocyanate, which can be cured at room temperature. It is useful in these technical fields as a material, flooring material, sealing material, injection material, adhesive and the like.

[0002]

2. Description of the Related Art Polyurethane resins take advantage of their excellent rubber elasticity, weather resistance, abrasion resistance, chemical resistance, and the like to make use of elastomers, caulks, paints, sealants, applied waterproof materials, floor materials, wall materials, and the like. It is widely used in various fields such as synthetic leather and adhesives.

[0003] Polyurethane resins used for waterproofing materials, floor coverings and the like are obtained by the polycondensation reaction of polyether polyols such as polyethylene glycol and polypropylene glycol, and dicarboxylic acids such as adipic acid with diols as polyol components as raw materials. Used polyester polyols and the like. These polyols are liquid at room temperature, and are used as a solventless thick film coating material in combination with a solventless organic isocyanate, but a polyurethane resin using a polyether polyol has a coating film. However, there is a problem that the polyester resin is deteriorated by heat and photo-oxidation or is easily corroded by an acid, and a polyurethane resin using a polyester polyol has a problem that its coating film is easily deteriorated by hydrolysis. In addition, many of these compositions contain an aromatic diamine or the like as a crosslinking agent, but due to the diamine present in the cured coating film, there is a problem that the weather resistance is reduced. .

[0004]

In applications requiring weather resistance, such as waterproofing materials and paints, acrylic urethane using a poly (meth) acrylate polyol having the above-mentioned problems as a polyol component as a polyurethane resin. A series resin is used. However, the conventional poly (meth) acrylate polyol has a high molecular weight and has no fluidity at room temperature, so that it is necessary to dilute the composition with a solvent in order to impart appropriate fluidity. Later, the solvent is volatilized and the skin becomes thin, and only a cured coating film having a thickness of at most several tens to several hundreds μm is obtained at a time. When considering the environmental aspect, the composition usually contains 40 to 60% by weight of a solvent, which is almost completely discharged into the atmosphere after drying. In recent years, there have been concerns about global pollution and effects on living organisms due to the release of organic solvents and cleaning solvents used in various industries, including the paint field, into the atmosphere. There is a need for paints. In addition, a polyurethane resin using a conventional poly (meth) acrylate polyol has insufficient elongation of a cured coating film. The present inventors have low viscosity and excellent fluidity, and the cured coating film has excellent heat resistance, weather resistance, acid resistance, water resistance and elongation, and to find a solventless composition capable of thick coating. We conducted intensive studies.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that to solve the above-mentioned problems, a two-part curable composition comprising a copolymer having a specific hydroxyl group and an organic polyisocyanate. Was found to be effective.
Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION

○ (A) component In the composition of the present invention, a copolymer having a hydroxyl group of the component (A) (hereinafter referred to as a hydroxyl group-containing copolymer)
At least one kind of (meth) acrylate having at least one hydroxyl group (hereinafter referred to as (meth) acrylate containing hydroxyl group) and a monomer having one ethylenically unsaturated group other than the (meth) acrylate (hereinafter referred to as ethylene) Copolymer with at least one kind of unsaturated unsaturated monomer).

As the hydroxyl group-containing (meth) acrylate, various ones can be used. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; Polyhydric alcohol mono- or poly (meth) acrylates such as erythritol tri (meth) acrylate and glycerin mono (meth) acrylate; and epoxides such as adducts of cyclohexene oxide with (meth) acrylic acid and (meth) acrylic acid. Adducts.

As the ethylenically unsaturated monomer, various ones can be used as long as they are other than the above-mentioned hydroxyl group-containing (meth) acrylate, such as styrene, acrylonitrile, methacrylonitrile, vinyl acetate and (meth) acrylate. Is mentioned. Specific examples of (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2- (meth) acrylate. Examples include ethoxyethyl (meth) acrylate and isobornyl (meth) acrylate.

The hydroxyl group-containing copolymer used in the present invention comprises:
It is necessary that 5% by weight or more of the hydroxyl group-containing (meth) acrylate is copolymerized based on the total amount of the hydroxyl group-containing (meth) acrylate and the ethylenically unsaturated monomer, and preferably 15 to 60% by weight. %, More preferably 20 to 50% by weight. If the copolymerization ratio of the hydroxyl group-containing (meth) acrylate is less than 5% by weight, the reaction with the organic polyisocyanate is insufficient, resulting in poor curing, and the resulting cured coating film has high chemical resistance, abrasion resistance and Inferior in tensile properties.

The number average molecular weight of the copolymer is 1,000 to 1,000.
Must be 20,000, preferably 1,000
〜１０10,000. If the number average molecular weight is less than 1,000, the composition cannot be thickly applied, or the cured coating film becomes inferior in flexibility.
If it exceeds, the viscosity will be high and workability such as coating will be poor. In the present invention, the number average molecular weight and the weight average molecular weight are values obtained by using tetrahydrofuran as a solvent and converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) into polystyrene.

As a copolymer of a hydroxyl group-containing (meth) acrylate and an ethylenically unsaturated monomer, a method known in the art, for example, a method using a hydroxyl group-containing (meth) acrylate in the presence of a polymerization solvent and a thermal polymerization initiator, Those produced by solution polymerization or the like in which an ethylenically unsaturated monomer is heated and stirred can be used. In this case, the reaction temperature depends on the monomer used,
The type of thermal polymerization initiator, decomposition temperature, or half-life, may be appropriately selected depending on the boiling point of the polymerization solvent and the like, but usually 50 to 120
C is appropriate. The thermal polymerization initiator is not particularly limited, and examples thereof include azonitrile-based initiators and peroxide-based initiators generally used in thermal polymerization. Examples of the azonitrile initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) and 2,2-′azobis (2,4-dimethylvaleronitrile) And the like, and examples of the peroxide-based initiator include hydrogen peroxide, di-t-butyl peroxide, and benzoyl peroxide. The amount of the thermal polymerization initiator used is 0.01 to 1 based on 100 parts by weight of the total amount of the hydroxyl group-containing (meth) acrylate and the ethylenically unsaturated monomer.
It is preferably 0 parts by weight. The polymerization solvent is not particularly limited, either, as long as it can dissolve the produced copolymer. For example, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, cellosolve acetate,
Examples include methyl propylene glycol acetate, carbitol acetate, acetate esters such as methyl propylene glycol acetate, carbitol acetate and ethyl carbitol acetate, and ketones such as acetone and methyl ethyl ketone. The amount of the polymerization solvent used is 10 to 10 as the solid content concentration of the obtained copolymer.
The amount is preferably 90% by weight. Further, in the present invention, since the molecular weight distribution of the obtained hydroxyl group-containing copolymer is reduced, a monomer mixture comprising a hydroxyl group-containing (meth) acrylate and an ethylenically unsaturated monomer, a polymerization solvent, and thermal polymerization start After the reaction is initiated by heating and stirring the reaction solution comprising the agent, a mixture comprising the monomer mixture, the polymerization solvent and the thermal polymerization initiator is dropped into the reaction solution to carry out polymerization.

A particularly preferred copolymer for the component (A) of the present invention is a copolymer obtained by continuously polymerizing a hydroxyl group-containing (meth) acrylate and an ethylenically unsaturated monomer at a high temperature of 150 to 350 ° C. It is a polymer. According to this high-temperature continuous polymerization method, a low-molecular-weight, low-viscosity hydroxyl-containing copolymer can be obtained, and the polymerization method does not require the use of a thermal polymerization initiator or uses a thermal polymerization initiator. Even in this case, the use of a small amount can provide the desired molecular weight copolymer,
Since a highly pure copolymer containing almost no impurities that generate radical species by heat or light can be obtained, a cured coating film of the composition can have excellent weather resistance. Further, a copolymer having a lower polydispersity than that obtained by conventional solution polymerization can be obtained.

As the high temperature continuous polymerization method, Japanese Patent Application Laid-Open No. 57-50217
No. 1, 59-6207, 60-215007, etc. may be used. For example, a pressurizable reactor is filled with a solvent, and after a predetermined temperature is set under pressure, a monomer comprising a hydroxyl group-containing (meth) acrylate, an ethylenically unsaturated monomer, and, if necessary, a polymerization solvent is used. There is a method in which the body mixture is supplied to the reactor at a constant supply rate, and an amount of the reaction solution corresponding to the supply amount of the monomer mixture is withdrawn. When a polymerization solvent is used, the solvent charged into the reactor at the start of the reaction and the polymerization solvent mixed with the monomer mixture may be the same or different. As the solvent or the polymerization solvent, those similar to those described in the solution polymerization can be used, and alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol can be used. The mixing ratio of the polymerization solvent is preferably 200 parts by weight or less based on 100 parts by weight of the monomer mixture. In addition, the monomer mixture may be blended with a thermal polymerization initiator, if necessary, and as the thermal polymerization initiator that can be used in this case, the same ones as those described in the solution polymerization can be used. . When the thermal polymerization initiator is blended with the monomer mixture, the blending amount may be 0.0 to 100 parts by weight of the monomer mixture.
It is preferably from 0.01 to 5 parts by weight. Reaction temperature is 15
The temperature is preferably from 0 to 350 ° C. If the temperature is lower than 150 ° C., the molecular weight of the obtained copolymer may be too large or the reaction rate may be slow. May be colored. The pressure depends on the reaction temperature and the boiling point of the monomer mixture and the solvent used, and does not affect the reaction, but may be any pressure that can maintain the reaction temperature. The residence time of the monomer mixture is 2
It is preferably up to 60 minutes. When the residence time is less than 2 minutes, when the unreacted monomer exceeds 60 minutes, productivity may be deteriorated.

It is preferable to mix a low molecular weight polyhydric alcohol with the component (A) if necessary, because the mechanical properties and the like of the obtained cured coating film can be improved. Specific examples of the low molecular weight polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, bisphenol A, trimethylolethane, trimethylolpropane, Glycerin and sorbitol. (A)
In the component, a preferable ratio in the case of blending a low molecular weight polyhydric alcohol is 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the hydroxyl group-containing copolymer.
Parts by weight. When the amount is less than 1 part by weight, the effect of improving the mechanical properties of the obtained cured coating film is not sufficient, and
If the amount is more than 0 parts by weight, the resulting cured coating film may be hard and brittle. The low molecular weight polyhydric alcohol is 2
More than one species may be used in combination.

Component (B) As the organic polyisocyanate that is the component (B) of the present invention, various organic polyisocyanates can be used, and those which do not need to be diluted with a solvent and which are liquid at room temperature are preferred. As organic polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, in terms of excellent weather resistance,
It is preferable to use hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like, and aliphatic organic polyisocyanates having no aromatic ring, such as burettes, isocyanurates and carbodiimide modified products thereof. Other than these, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, liquid diphenylmethane diisocyanate, tolylene diisocyanate, tolidine diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, and the like, and their burettes, isocyanurates, and carbodiimides Various organic polyisocyanates, such as organic materials, can be used. These organic polyisocyanates may be used in combination of two or more.

The catalyst The two-part curable composition of the present invention can obtain a polyurethane resin of a cured coating film by a urethanization reaction when the components (A) and (B) are mixed. It is preferable to add a catalyst to the composition because the composition can be accelerated. As the catalyst, triethylamine, NN-dimethylcyclohexylamine, N, N, N'N'-tetramethylethylenediamine, N, N, N'N'-tetramethylpropane 1,3-diamine,
N, N, N'N'-tetramethylhexane-1,6-diamine, N, N,
N ', N``N''-pentamethyldiethylenetriamine, N, N,
N ', N``N''-pentamethyldipropylene-triamine,
Tetramethylguanidine, triethylenediamine, N, N '
-Dimethylpiperazine, N, -methyl, N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N
(N'-dimethylaminoethyl) -morpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethyl-ethanol, N-methyl-N '-(2hydroxy Ethyl) -ethanolamine, N-methyl-N '-(2-hydroxyethyl) -piperazine, N- (2-hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether and ethylene glycol bis (3-dimethyl) -Amine catalysts such as aminopropyl ether; organic metal compounds such as lead octenoate, lead octylate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide and dioctyltin thiocarboxylate And calcium carbonate and sodium bicarbonate. Among these, the use of an organometallic compound can be used with the component (A).
(B) It is preferable because the reactivity of the component is excellent. The amount of these catalysts is preferably 10 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of the hydroxyl group-containing copolymer. When compounding a catalyst into the composition,
It is preferable to mix a catalyst with the component (A) and then mix the component (A) and the component (B) containing the catalyst, since the reaction between the organic polyisocyanates can be prevented.

Other ingredients In addition to the above-mentioned components, fillers such as barium sulfate, silicon oxide, talc, mica, kaolin clay and calcium carbonate, phthalocyanine blue, Coloring pigments such as phthalocyanine green, titanium oxide, carbon black and iron oxide; antifoaming agents such as silicon-based and acrylic-based; hydrolysis inhibitors such as carbodiimide-based, azodicarboxylic ester-based and fatty acid amide-based, Antioxidants such as phenolic and aromatic diamines with steric hindrance, UV absorbers such as benzotriazole, benzophenone and salicylic acid, defoamers such as silicone, acrylic and mineral, and leveling agents Etc. can be blended. When these are compounded, the mixing ratio of the hydroxyl group-containing copolymer is 100%.
It is preferably 100 parts by weight or less based on parts by weight. When compounding these other components into the composition, first mix the other components with the component (A), and then mix the components (A) and (B) containing the other components. This is preferable because foaming of the composition caused by the reaction between the water contained in the other components and the organic polyisocyanate can be prevented.

Method of Use The two-part curable composition of the present invention is prepared by mixing the components (A) and (B) before use as in the case of the conventional two-part curable urethane composition. It may be applied, injected or filled. The component (A) is preferably subjected to a dehydration operation after being blended with a catalyst and / or other blends if necessary, and before blending with the organic polyisocyanate (B). Performing the dehydration operation is preferable because foaming of the composition resulting from the reaction between the water contained in the component (A) and the organic polyisocyanate can be prevented. As a method of the dehydration operation, vacuum dehydration and the like can be mentioned. A preferable ratio of the component (A) and the component (B) is a ratio of the total amount of the isocyanate groups of the component (B) to the total amount of the hydroxyl groups in the component (A),
NCO / OH is preferably 0.5 to 2 (molar ratio), more preferably 0.7 to 1.5. When this ratio is less than 0.5, the strength of the cured coating film may not be sufficient. On the other hand, when this ratio exceeds 2, as the component (B), relatively relatively reactive aromatic aromatic polyisocyanate is used. When using an aliphatic organic polyisocyanate inferior in properties, the composition may cause poor curing, while when using an aromatic organic polyisocyanate having relatively high reactivity, the cured coating film becomes brittle. There are cases.

Examples of the method of applying the composition include a method using a roller, a lake, a trowel, a spray and the like.
Examples of the injection or filling method include a method using a caulking gun, a spatula, a spatula, an iron and the like.

The composition of the present invention can be used for various applications such as coating materials such as paints, waterproof materials, wall materials and floor coating materials, sealing materials, injection materials and adhesives.

[0021]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. In the following, parts and% are based on weight. Production Example 1 (Production of Hydroxyl-Containing Copolymer by Continuous High-Temperature Polymerization) A 6000 ml capacity pressurized stirred tank reactor equipped with an electric heater was filled with diethylene glycol monoethyl ether, the temperature was raised to 250 ° C, and the pressure was increased. The pressure was maintained at 25-27 kg / cm ² by gauge with a regulator. Then
Hydroxyl-containing (meta) while keeping reactor pressure constant
Monomer mixture consisting of 16 parts of 2-hydroxyethyl methacrylate and 20 parts of 2-hydroxyethyl acrylate as acrylate, 54 parts of 2-ethylhexyl acrylate as ethylenically unsaturated monomer and 10 parts of styrene
A-1 was fed at a constant feed rate (500 g / min, residence time: 1).
At 2 minutes), continuous supply from the raw material tank to the reactor was started, and a reactant corresponding to the supply amount of the monomer mixture A-1 was continuously extracted from the outlet. Immediately after the start of the reaction, after the reaction temperature once decreased, a rise in the temperature due to the heat of polymerization was recognized.
Was held. The point at which the temperature was stabilized from the start of the supply of the monomer mixture A-1 was defined as the starting point of the withdrawal of the reaction solution.
As a result of continuing the reaction for 5 minutes, 17.5 kg of the monomer mixture
A-1 was supplied, and 17.4 kg of a reaction solution was recovered. The reactor was introduced into a thin-film evaporator, and volatile components such as unreacted monomers were separated to obtain 15.5 kg of a concentrated solution (copolymer B-1). According to gas chromatography, no unreacted monomer was present in the concentrated liquid. The number average molecular weight (hereinafter abbreviated as Mn) of the copolymer B-1 in which the molecular weight determined by GPC is 2,000 and the weight average molecular weight (hereinafter abbreviated as Mw), using tetrahydrofuran as a solvent, and the molecular weight obtained by GPC converted into polystyrene.
Was 3,600 and the polydispersity was 1.80. The concentration of the hydroxyl group in the concentrated solution was 3.09 meq / g.

Production Example 2 (Production of Hydroxyl-Containing Copolymer by Continuous High-Temperature Polymerization) The same reactor as in Production Example 1 was filled with diethylene glycol monoethyl ether and kept under the same conditions as in Production Example 1. Then, 2- (meth) acrylate containing hydroxyl group
A simple composition comprising 10 parts of hydroxyethyl methacrylate and 20 parts of 2-hydroxyethyl acrylate, 70 parts of 2-ethylhexyl acrylate as an ethylenically unsaturated monomer, and 1 part of di-t-butyl peroxide as a polymerization initiator. The reaction was started under the same conditions as in Production Example 1 except that the monomer mixture A-2 was used and the feed rate was 500 g / min (residence time: 12 minutes). Immediately after the start of the reaction, after the reaction temperature once decreased, a rise in temperature due to the heat of polymerization was observed.
244 ° C was maintained. The time at which the temperature was stabilized from the start of the supply of the monomer mixture A-2 was taken as the starting point of the withdrawal of the reaction solution, and as a result of continuing the reaction for 40 minutes, 20.0 kg of the monomer mixture A-2 was supplied. 19.9 kg of the reaction solution was recovered. The reactor was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated, and 17.9 kg of a concentrated solution (copolymer B-
2) Got it. According to gas chromatography, no unreacted monomer was present in the concentrated liquid. The molecular weight of copolymer B-2 determined in the same manner as in Production Example 1 was Mn of 2,900,
Mw was 4,900 and polydispersity was 1.70.
Further, the hydroxyl group concentration of the concentrated solution was 2.10 meq / g.

Production Example 3 (Production of a hydroxyl group-containing copolymer by solution polymerization) 10 parts of hydroxyethyl methacrylate and 20 parts of hydroxyethyl acrylate as the hydroxyl group-containing (meth) acrylate, and 2-ethylhexyl acrylate as the ethylenically unsaturated monomer 70 parts of a monomer mixture
A-3. In a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen replacement and a stirrer, 15 parts of the monomer mixture A-3, 100 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) and Charge 1 part of 2,2'-azoisobutyronitrile
At ℃, the polymerization reaction was started. After this, the monomer mixture
A polymerization reaction was carried out by continuously dropping 31 parts of a solution composed of 85 parts of A-3, 25 parts of MIBK and 6 parts of 2,2'-azobisisobutyronitrile over 6 hours. The solvent was distilled off from the obtained reaction solution under reduced pressure to obtain a copolymer B-3. The molecular weight of copolymer B-3 determined in the same manner as in Production Example 1 was Mn of 8,80.
0, Mw was 19,000, and the polydispersity was 2.2. The hydroxyl group concentration was 2.60 meq / g.

Example 1 100 parts of B-1 obtained in Production Example 1, 1 part of a polysiloxane-based defoamer BYK-066 (manufactured by Tetsutani Corporation), 2 parts of titanium oxide and di-n-butyl Add 0.001 part of tin dilaurate to the planetary mixer, stir at room temperature for 15 minutes,
Subsequently, while kneading at 100 ° C., a dehydration operation was performed for 1 hour under vacuum to obtain a mixture C-1 as the component (A).

Next, 100 parts (3.00 meq / g) of C-1 and (B)
Isocyanurate of hexamethylene diisocyanate (Sumidur N3500, NCO group content 5.
14meq / g, manufactured by Sumitomo Bayer Urethane Co., Ltd.]
An O / OH equivalent ratio of 1.05 was added and the mixture was sufficiently stirred to produce a composition. Immediately put the obtained composition on a Teflon plate,
It was allowed to stand at 20 ° C. and 60% humidity for curing. The average thickness of the cured coating film after 168 hours was 1.1 mm.

The obtained composition and cured coating film were evaluated according to the following methods. Table 1 shows the results.

Evaluation: Viscosity The viscosity of the composition immediately after mixing the components (A) and (B) was measured at 25 ° C.
Was measured with a B-type viscosity mold.

Tensile physical properties The obtained cured coating film was subjected to a tensile speed of 200 mm / according to JIS K 6301.
The tensile strength and elongation were measured in minutes.

Film-forming property The composition was poured onto a mortar plate at 25 ° C. so as to have a dry film thickness of about 3 mm, and was cured by reaction. The obtained cured coating film was visually observed. In Table 1, ○, Δ, and × have the following meanings. ：: No abnormality in appearance, Δ: Slight wrinkles and the like are observed in appearance. ×: Abnormalities such as cracks are observed in the appearance.

Weather resistance The obtained cured coating film was treated at 63 ° C. and 1 ° C. using a carbon arc sunshine weather meter manufactured by Suga Test Instruments Co., Ltd.
Tested for 000 hours. The color difference of the cured film after the test was evaluated by ΔE and gloss retention at 60 ° C. In Table 1, ◎, △, Δ, and × have the following meanings. ΔE: ；; <1, ；; 1-2, ；; 2-3, ×;> 3 Gloss retention: ◎;> 90%, ；; 70-90%, Δ; 40-70%, ×; <40%

Chemical resistance The obtained cured coating film was immersed in the following chemicals at room temperature for 168 hours, and the appearance of the cured coating film was observed.・ 40% sodium hydroxide aqueous solution ・ 20% sulfuric acid aqueous solution ・ 5% acetic acid aqueous solution ・ toluene In Table 1, ◎, ○, △, × indicate the following meanings. : Almost no change, 光 沢: gloss and color slightly changed,
Δ: Gloss and color clearly changed, ×: Gloss and color significantly changed

[0032]

[Table 1]

Example 2 The procedure of Example 1 was repeated except that 100 parts of B-1 and 10 parts of 1,4-butanediol obtained in Production Example 1 were used.
A mixture C-2 as the component (A) was obtained. Next, a composition was prepared in the same manner as in Example 1 except that 100 parts (4.70 meq / g) of C-2 was used and the NCO / OH equivalent ratio was changed to 1.05. When the obtained composition was cured on a Teflon plate in the same manner as in Example 1, the average thickness of the cured coating film after 168 hours was 1.1 mm. The obtained composition and cured coating film were evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 The procedure of Example 1 was repeated except that 100 parts of B-2 and 10 parts of 1,4-butanediol obtained in Production Example 2 were used.
A mixture C-3 as the component (A) was obtained. Next, a composition was prepared in the same manner as in Example 1 except that 100 parts (4.07 meq / g) of C-3 was used and the NCO / OH equivalent ratio was changed to 1.05. When the obtained composition was cured on a Teflon plate in the same manner as in Example 1, the cured coating film after 168 hours had no tack and the average film thickness was 1.0 mm. The obtained composition and cured coating film were evaluated in the same manner as in Example 1.
Table 1 shows the results.

Example 4 Except that 100 parts of B-3 obtained in Production Example 3 was used,
A mixture C-4 as the component (A) was obtained in the same manner as in Example 1. Next, 100 parts (3.80meq / g) of C-4 were used and NCO /
A composition was produced in the same manner as in Example 1 except that the OH equivalent ratio was changed to 1.05. When the obtained composition was cured on a Teflon plate in the same manner as in Example 1, the cured coating film after 168 hours had no tack and the average film thickness was 1.0 mm. About the obtained composition and the cured coating film, Example 1
The evaluation was made in the same manner as in Table 1 shows the results.

Example 5 The procedure of Example 1 was repeated except that 100 parts of B-3 and 10 parts of 1,4-butanediol obtained in Production Example 3 were used.
A mixture C-5 as the component (A) was obtained. Next, a composition was prepared in the same manner as in Example 1 except that 100 parts (3.80 meq / g) of C-5 was used and the NCO / OH equivalent ratio was changed to 1.05. When the obtained composition was cured on a Teflon plate in the same manner as in Example 1, the cured coating film after 168 hours had no tack and the average film thickness was 1.0 mm. The obtained composition and cured coating film were evaluated in the same manner as in Example 1.
Table 1 shows the results.

Comparative Example 1 12 parts of polypropylene glycol (manufactured by Asahi Glass Co., Ltd.) having an Mn of about 2,000 and 12 parts of 3,3′-dichloro-4,4′-diaminodiphenylmethane (manufactured by Ihara Chemical Co., Ltd.) And 36 parts of dioctyl phthalate, 37 parts of calcium carbonate, 3 parts of titanium oxide and 0.01 part of lead octenoate were mixed in the same manner as in Example 1. To this mixture, tolylene diisocyanate-modified polypropylene glycol [Desmodur E14: manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO group content: 0.833 meq / g] is added at an NCO / OH equivalent ratio of 1.05, and the mixture is sufficiently stirred to obtain a composition. Was manufactured. When the obtained composition was cured on a Teflon plate in the same manner as in Example 1, the cured coating film after 168 hours had no tack and the average film thickness was 1.1 mm. The obtained composition and cured coating film were evaluated in the same manner as in Example 1. Table 2 shows the results.

COMPARATIVE EXAMPLE 2 As a solvent-type acrylic polyol used for general purposes, its monomer composition was 49 parts of n-butyl methacrylate,
60% acetic acid of a hydroxyl-containing copolymer having 23 parts of styrene, 21 parts of methyl methacrylate, 6 parts by weight of hydroxypropyl methacrylate and 1 part by weight of acrylic acid, and having Mn of 27,000 and Mw of 65,800. A butyl solution was used. The hydroxyl group-containing copolymer itself is a solid. This solvent-type acrylic polyol and Sumidur N3500 were added and mixed at an NCO / OH equivalent ratio of 1.05 to produce a composition. The obtained composition was cured by standing on a Teflon plate under the same conditions as in Example 1 for 168 hours, and further left for 84 hours at 50 ° C. and 60% humidity. The average thickness of the coating film was only 120 μm, and only a thin cured coating film was obtained. The obtained composition and cured coating film were evaluated in the same manner as in Example 1. Table 2 shows the results.

[0039]

[Table 2]

[0040]

The two-part curable composition of the present invention is excellent in workability due to its low viscosity, and can be used as a solvent-free composition, so that it has no problems such as odor and the cured coating film can be made thick. The cured film obtained is excellent in heat resistance, weather resistance, chemical resistance and elongation, and is useful in various industrial fields such as paints, waterproof materials, floor materials, sealing materials, injection materials and adhesives. Things.

Claims (3)

[Claims] 1. A two-part curable composition comprising the following components (A) and (B). (A) at least one kind of (meth) acrylate having at least one hydroxyl group and at least 5% by weight and at least one kind of monomer having an ethylenically unsaturated group other than the (meth) acrylate;
A copolymer having a number average molecular weight of 1,000 to 20,000 and a copolymer of 5% by weight or less (B) an organic polyisocyanate 2. The two-part curable composition according to claim 1, wherein the component (A) further contains 1 to 50 parts by weight of a low molecular weight polyhydric alcohol based on 100 parts by weight of the copolymer. 3. The copolymer of component (A) is 150 to 3
The two-part curable composition according to claim 1 or 2, which is obtained by continuous polymerization at a copolymerization temperature of 50 ° C.