JPH11147988A - Urethane / acrylic resin composition, method for producing the same, molded article or molded part - Google Patents

Abstract

(57) [Problem] To provide a polyurethane-containing acrylic resin composition which is excellent in transparency and has significantly improved impact resistance and tensile elongation. SOLUTION: This is a composition comprising 5 to 50% by weight of a modified polyurethane component (A) and 50 to 95% by weight of an acrylic polymer component (B) containing 50% by weight or more of a methyl methacrylate unit. It has a microphase-separated structure in which particles of the acrylic polymer component (B) are dispersed in the continuous phase of (A), and at least a part of the modified polyurethane component (A) and at least a part of the acrylic polymer component ( A resin composition obtained by chemically bonding B). A molded article or molded part comprising the resin composition. A syrup comprising 5 to 50% by weight of the modified polyurethane (a) and 50 to 95% by weight of an acrylic monomer (b) containing at least 50% by weight of methyl methacrylate is polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to weather resistance, impact resistance,
The present invention relates to a polyurethane-containing acrylic resin composition having excellent transparency, elongation, and heat deformation resistance.

[0002]

2. Description of the Related Art Acrylic resins represented by poly (methyl methacrylate) are excellent in transparency and weather resistance and have a beautiful appearance, so that they can be used for signboard supplies, display supplies, lighting supplies, interior supplies, building parts, It is widely used in transport equipment parts, electronic equipment parts, medical equipment parts, equipment parts, optical parts, transportation parts, aquarium supplies, sanitary supplies, game supplies and the like.

[0003] On the other hand, acrylic resins are molding materials which are excellent in transparency and weather resistance and have a beautiful appearance, but have a drawback that they are inferior in impact resistance. In order to improve impact resistance, a method of blending a diene-based rubber containing butadiene as a main component has conventionally been adopted, but a blend obtained by such a method has a large impact strength,
Due to the residual double bond based on butadiene in the rubber component,
It is known that weather resistance and heat resistance deteriorate. Therefore, as a method of imparting impact resistance while maintaining weather resistance,
A method of blending an acrylic rubber such as a polyacrylic acid alkyl ester-styrene copolymer with a thermoplastic hard resin has been used. However, in the method of blending an acrylic rubber, the effect of improving the impact resistance is smaller than in the case of blending a butadiene rubber, and a large amount of a rubber component must be blended in order to obtain a desired impact strength. As a result, properties such as heat deformation resistance, scratch resistance, and rigidity inherent in the hard resin are impaired.

Polyurethane is a material whose physical properties can be varied widely from hard to soft by selecting raw materials to be used. Poly (tetramethylene oxide) diol and poly (ε-caprolactone) diol are used as a polyol component as a raw material. It is known that when a polymer having a polymer segment having a glass transition temperature of room temperature or lower is used, a polyurethane rubber excellent in elasticity and elasticity, excellent in durability and abrasion resistance can be obtained. It can be a rubber source effective for improving the impact resistance of an acrylic resin.

[0005] For example, Japanese Patent Publication No. 48-42956 discloses radical polymerization of a syrup-like mixture comprising a monomer component having methyl methacrylate as a main constituent and an alkenyl group bonded to both ends of polyurethane. There has been proposed a method for producing an acrylic resin cast plate having excellent impact resistance. This method also suggests the possibility of development in the field of liquid resins represented by epoxy resins represented by unsaturated polyester resins and epoxy resins of polyurethane-containing acrylic syrup. In particular, while unsaturated polyester resins and epoxy resins generally have the disadvantage of brittleness of cured products, the syrup-like products used in this method are extremely characteristic in that they give cured products with excellent impact resistance. It is considered to be a suitable liquid resin.

In Japanese Patent Application Laid-Open No. 3-54217,
Simultaneously improves impact resistance and heat deformation resistance by adding a low molecular weight crosslinking agent and a chain transfer agent such as mercaptan to a polyurethane-containing syrup, or adding a low-molecular crosslinking agent to a prepolymerized polyurethane-containing syrup and curing. doing.

[0007]

The above-mentioned method shows that polyurethane is an effective rubber source for improving the impact resistance of a cured product of an acrylic liquid syrup. Sex has not yet reached a satisfactory level. Further, since the viscosity of the polyurethane-containing acrylic syrup (polyurethane content 15%) in these publications is as low as about 50 to 100 cps (25 ° C.), the molecular weight of the polyurethane itself used is quite small.

On the other hand, in order for the acrylic liquid resin (syrup) to be useful for applications such as casting and FRP, or as a molding material, it is necessary to further improve the impact resistance of the cured product. Improvement of tensile elongation for improving cracking property is also an important required performance.

An object of the present invention is to provide a polyurethane-containing acrylic resin composition which is excellent in transparency, and further has remarkably improved impact resistance and tensile elongation.

[0010]

Means for Solving the Problems The present inventors pay attention to the molecular weight of polyurethane, and by using a high-molecular-weight modified polyurethane copolymerizable with an acrylic monomer, a phase separation structure of a cured product is developed. The present invention has been further achieved by forming a morphology having a microphase-separated structure (elastomer matrix structure) in which acrylic polymer particles are dispersed in a continuous phase of an elastomer composed of a polyurethane component.

That is, the gist of the present invention is to provide an acrylic polymer component (B) containing 5 to 50% by weight of a modified polyurethane component (A) and 50% by weight or more of a methyl methacrylate unit.
A composition comprising 95% by weight, having a microphase-separated structure in which particles of an acrylic polymer component (B) are dispersed in a continuous phase of a modified polyurethane component (A), and at least a part of the modified polyurethane component. The resin composition is obtained by chemically bonding (A) and at least a part of the acrylic polymer component (B), and is present in a molded article or molded part made of the resin composition.

Further, the gist of the present invention is to provide a modified polyurethane (a) having an alkenyl group at the terminal of a polymer chain having a weight average molecular weight of 100,000 or more, 5 to 50% by weight, and an acrylic monomer containing 50% by weight or more of methyl methacrylate. Monomer (b) 5
The method for producing a resin composition according to the above, wherein the polyurethane-containing acrylic syrup comprising 0 to 95% by weight is cured by a radical polymerization method.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The modified polyurethane component (A) comprises:
It is a component derived from the modified polyurethane after the alkenyl group part of the raw material of the modified polyurethane having an alkenyl group at the polymer chain terminal is chemically bonded to the polymerizable unsaturated bond group of the raw material of the acrylic polymer component (B). In the resin composition, the modified polyurethane component (A) acts as an elastomer source, and its morphology forms an elastomer matrix structure in which the elastomer component forms a continuous phase.

The mechanical properties of the resin composition having such a morphology include the degree of phase separation between the modified polyurethane component (A) forming a continuous phase and the acrylic polymer component (B) forming a dispersed phase, It is greatly affected by the weight average molecular weight of the modified polyurethane component (B) forming a continuous phase. Therefore, in order to increase the elasticity and elasticity of the resin composition to a high value, the modified polyurethane component (A) having a higher molecular weight and excellent mechanical properties forms a continuous phase and forms an acrylic phase which forms a dispersed phase. It is desirable that the phase separation structure with the coalesced component (B) is sufficiently developed. Therefore, the weight average molecular weight of the component (A) of the polyurethane is preferably 100,000 or more, more preferably 150,000 or more.

The acrylic polymer component (B) is a component comprising a polymer containing 50% by weight or more of methyl methacrylate units, and is a component constituting a portion of the resin composition excluding the component (A). is there. This resin composition has a microphase-separated structure in which particles of the component (B) having a particle diameter of about several tens nm to several μm are dispersed in the component (A) forming a continuous phase.

In the resin composition, at least a part of the modified polyurethane component (A) and at least a part of the acrylic polymer component (B) are chemically bonded. It is not necessary that all of the ends of the polymer chains of component (A) are chemically bonded to the polymer chains of component (B), but the ends of the polymer chains of component (A) may be substantially all or most of them. It is preferably chemically bonded to the polymer chain of the component (B). A typical chemical bond structure is a crosslinked structure in which the polymer chain of the component (B) is bridged with the polymer chain of the component (A).

Hereinafter, a typical production method of the resin composition will be described. The resin composition of the present invention is, for example, an acrylic monomer containing 5 to 50% by weight of a modified polyurethane (a) having an alkenyl group at a polymer chain terminal and having a weight average molecular weight of 100,000 or more, and 50% by weight or more of methyl methacrylate. Body (b) 5
It can be produced by curing a polyurethane-containing acrylic syrup (hereinafter appropriately referred to as “syrup”) consisting of 0 to 95% by weight by a radical polymerization method.

The modified polyurethane serving as a raw material of the modified polyurethane component (A) preferably has an alkenyl group at a polymer chain terminal. Further, from the viewpoint of improving the impact resistance of the obtained resin composition, those having a glass transition temperature Tg of 25 ° C. or less are preferable. Tg is more preferably 0 ° C or lower, and further preferably -20 ° C or lower. When the temperature is -20 ° C or lower, a clearly good impact resistance improving effect can be obtained.

The raw materials of the modified polyurethane include 1) an organic polyisocyanate, 2) an organic polyol, and 3) a compound having an alkenyl group copolymerizable with methyl methacrylate and an active hydrogen atom capable of reacting with the isocyanate group, or methacryl. Three components of a compound having an alkenyl group and an isocyanate group copolymerizable with methyl acid are used.

Examples of the organic isocyanate include commercially available aliphatic or aromatic organic diisocyanates. That is, tolylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and the like can be used. These can be used alone or in combination of several kinds.

It is preferable to use an organic polyol having a polymer segment having a glass transition temperature of 25 ° C. or lower in the molecular structure. Further, the molecular weight of the organic polyol is preferably 500 or more, and 500 to 20.
More preferably, it is 00. When such an organic polyol is used, a resin composition having excellent impact resistance and tensile elongation can be obtained.

Commercially available organic polyols can be used. That is, poly (oxyethylene) diol, poly (oxypropylene) diol, poly (oxytetramethylene) diol, (propylene oxide-tetrahydrofuran copolymer) diol, poly (ethyleneadipate) diol, poly (tetramethyleneadipate) diol, (Ethylene adipate-propylene adipate copolymer) diol, poly (ε-caprolactone) diol, polybutadiene diol (a main component of which is a 1,2-adduct), poly (dimethylsiloxane)
Examples thereof include diols, polycarbonate diols, and polyacryl polyols (butyl acrylate is a main component). These can be used alone or in combination of several kinds.

Polyurethane can be synthesized by a polyaddition reaction between these organic polyisocyanates and organic polyols. The blending ratio of the organic polyisocyanate and the organic polyol is determined so that the molar ratio of the isocyanate group to the hydroxyl group is in the range of 1/2 to 2, and any one of the functional groups is present in an excessive amount. A more preferable mixing ratio of the organic polyisocyanate and the organic polyol for synthesizing a high-molecular-weight polyurethane is such that the molar ratio of the isocyanate group to the hydroxyl group is 0.8 to 1.2. In each case, the weight average molecular weight of the modified polyurethane is 1
It is preferably at least 100,000, and more preferably at least 150,000.

The use of a high-molecular-weight modified polyurethane promotes the phase separation between the modified polyurethane component (A) and the acrylic polymer component (B), and the acrylic polymer is contained in the continuous phase of the modified polyurethane component (A). It works advantageously for forming a microphase-separated structure in which particles of the coalesced component (B) are dispersed. In the resin composition, since the modified polyurethane component (A) acts as an elastomer source, the use of the modified polyurethane having a high molecular weight allows the resin composition to exhibit excellent impact resistance and tensile elongation.

When the modified polyurethane is linear, the viscosity of the syrup is greatly affected by the weight-average molecular weight of the modified polyurethane, although there are some differences depending on the composition.
For example, regarding the viscosity of a syrup having a polyurethane content of 15% at 25 ° C., when the weight average molecular weight of the polyurethane is about 60,000, the viscosity of the syrup is about 100 cps. When the weight average molecular weight is about 100,000 and about 150,000, the syrup viscosity is about 150 cps and about 250 cps, respectively. From this, in order to obtain a cured product having remarkable impact resistance and tensile elongation, the viscosity of the syrup is preferably 150 cps or more, and 250 cps or more.
More preferably, it is not less than ps.

Although the syrup viscosity significantly varies depending on the concentration of the polyurethane, the syrup viscosity of 50 cps (25 ° C.) or less at any polyurethane concentration is not preferable because sufficient impact resistance cannot be obtained.

The high molecular weight modified polyurethane can be synthesized in the presence or absence of a solvent. However, in the non-solvent system, the reaction is difficult to control because the exothermic reaction is severe, and a side reaction is likely to occur. The synthesis is preferably performed in a monomer (solvent) containing methyl methacrylate as a main component. In this case, there is an advantage that a step of dissolving a high-molecular-weight modified polyurethane in the monomer can be omitted. However, in this synthesis method, there is a possibility that the water content in the solvent significantly impairs the increase in the molecular weight and causes a reduction in the reaction rate. Therefore, in order to more reliably achieve a high molecular weight in the presence of a solvent, it is preferable to synthesize in a monomer containing methyl methacrylate as a main component that has been sufficiently dehydrated and purified, and the urethane concentration in the reaction solution is preferably adjusted. It is more preferable that the composition is made as high as possible. Such a synthesis method is very effective not only in reducing the effect of water in the solvent but also in increasing the reaction rate.

As the dehydration purification (drying) method of the solvent, a sufficiently effective effect can be obtained by a known dehydration purification method, for example, a dehydration purification method using a molecular sieve.

It is effective to add a known catalyst for synthesizing urethane such as dibutyltin dilaurate or triethylamine to increase the reaction rate.

Also, a method of reacting while slowly dripping excess one of the organic polyisocyanate and the organic polyol is particularly effective for the synthesis of a high molecular weight polyurethane. At the terminal of the molecular chain of the polyurethane synthesized in this way, the functional group used in excess exists.

In the present invention, it is preferable to use a compound having an alkenyl group at a polymer chain terminal as the modified polyurethane. Since this alkenyl group can be copolymerized with methyl methacrylate, the modified polyurethane chemically bonds to the methyl methacrylate unit during curing of the syrup, and blocks the modified polyurethane component (A) and the acrylic polymer component (B). A polymer is formed, the interface strength between the urethane phase and the acrylic phase is improved, and a tough resin composition is obtained.

When an isocyanate group is present at the molecular chain end of the polyurethane, a vinyl compound having an active hydrogen atom is used. When a hydroxyl group is present at the molecular chain end of the polyurethane, a vinyl compound having an isocyanate group is used. By bonding to the polyurethane,
A polyurethane having an alkenyl group at a molecular chain terminal can be synthesized. Since the total number of molecular chain terminals decreases as the urethane becomes higher in molecular weight, it is preferable to use a dehydrated and purified vinyl compound to ensure that the reaction proceeds.

The vinyl compounds used for such purposes include acrylic acid, methacrylic acid, acrylic acid-β
-Hydroxyethyl, -β-hydroxyethyl methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, -β-isocyanatoethyl methacrylate, methacryloyl isocyanate and the like.

The molecular structure of the high molecular weight modified polyurethane in the present invention may have a crosslinked structure as long as it is soluble in an acrylic monomer, but it is linear and has an alkenyl group at both ends. Are preferred. If the molecular chain between the crosslinking points of the high molecular weight modified polyurethane is too short, the formation of the microphase-separated structure of the cured product becomes insufficient, and the cured product may not be able to obtain excellent impact resistance and improved tensile elongation. . When the molecular chain between crosslinking points of the high-molecular-weight modified polyurethane is sufficiently long, that is, when the molecular weight of the modified urethane is linear,
The cured product forms a developed microphase-separated structure, and a resin composition having excellent elasticity and elasticity can be obtained.

The syrup of the present invention can be obtained by uniformly mixing the thus obtained modified polyurethane and a monomer component containing 50% by weight or more of methyl methacrylate.

Monomers which can be used in a mixture with methyl methacrylate in a range of 50% by weight or less include methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, methacrylic acid. And non-crosslinkable monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, maleic anhydride, and cyclohexylmaleimide.

It is also possible to use a crosslinkable monomer having a plurality of alkenyl groups having a relatively low molecular weight and a chain transfer agent typified by mercaptan and to add them in an appropriate blend, and to cure the syrup. It is extremely effective in improving the impact resistance, heat deformation resistance, and transparency of the resin composition obtained in this manner or simultaneously.

In the present invention, the effect of the progress of the phase separation between the modified polyurethane and the acrylic polymer, which proceeds during the curing process of the syrup, on the mechanical, thermal, and optical properties of the cured product (resin composition) is not affected. large. The phase separation structure can be controlled by controlling the molecular weight of the modified polyurethane, the cross-linking monomer or the chain transfer agent alone or in combination, and controlling the curing speed by the polymerization temperature and the like.

When the curing rate is reduced, the polymerization-induced phase separation accompanying the formation of the acrylic polymer is sufficiently developed, and the cured product has excellent impact resistance and tensile elongation, but the rigidity tends to decrease. . Since the addition of a chain transfer agent such as mercaptan not only slows down the curing rate but also lowers the grafting efficiency between the modified urethane and the acrylic polymer,
A remarkable phase separation structure is caused, and the cured product exhibits excellent impact resistance and tensile elongation, and the rigidity is significantly reduced. However, by using a small amount of a crosslinkable monomer in combination, excellent impact resistance can be developed without impairing the rigidity.

Examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like. Further, as the crosslinkable monomer, for example, ethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate and the like.

In a preferred embodiment, the syrup has a molecular weight of 10 having a plurality of alkenyl groups per 100 parts by weight.
0 to 25 parts by weight of a monomer which is not more than 00, a chain transfer agent 0
One example is a production method in which 1 part by weight is blended to carry out radical polymerization.

The content of the modified polyurethane in the syrup is 5 to 5.
Preferably it is present in a proportion of 50% by weight. When the content of the modified polyurethane is less than 5% by weight, the impact resistance of the cured product is insufficient, and when it exceeds 50% by weight, the viscosity of the syrup becomes extremely high, and it is difficult to handle as a liquid material. In addition, the rigidity of the cured product is significantly impaired. A more preferred modified polyurethane content is 10 to 30.
% By weight.

For curing the syrup, it is preferable to use a known radical initiator having a medium to low temperature activity. 2,
2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 ′ Azo initiators such as azobis (cyclohexane-1-carbonitrile) and peroxide initiators such as lauroyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, etc. , As well as mixtures of several of these. Curing using a redox initiator obtained by combining a peroxide initiator and a reducing agent is also particularly effective for curing in a short time. For example, a combination of benzoyl peroxide and dimethylaniline, and a combination of methyl ethyl ketone peroxide and cobalt naphthenate are exemplified.

The curing temperature is appropriately set according to the reactivity of the initiator system. By selecting the initiator system and setting the curing temperature,
The curing time of the syrup can vary from minutes to tens of hours.

Examples of the molding method used at the time of curing include a mold polymerization method in a cell composed of a tempered glass plate or a polished metal plate and a soft polyvinyl chloride gasket, and a continuous plate production method on a continuous belt. Is done. It is also possible to form pellets by continuous bulk polymerization. Furthermore, if you want to obtain molded products of various shapes, casting molding method, centrifugal molding method using various molds and dies, resin injection method, filament winding molding method, pultrusion molding method, hand lay-up molding method A known molding method such as a spray-up molding method can be used.

By the above method, a resin composition having improved impact resistance, heat deformation resistance, transparency and the like can be obtained.

The syrup is cured by the radical polymerization method in two stages of a partial polymerization treatment and a curing treatment.
A method in which the syrup partially polymerized in the step is cured in the second step under the condition that the crosslinkable monomer and the chain transfer agent are present in appropriate amounts can also be adopted.

Advantages of performing the partial polymerization treatment include:
During the curing process, the desired viscosity can be imparted to the syrup, the uniformity of various fillers can be increased, and the polymerization shrinkage can be reduced. By using this method, the SMC molding method, BMC molding method, etc. A molding method characterized by high productivity can be applied to syrup. When it is desired to impart viscosity to the syrup or reduce the shrinkage, a method in which a resin such as polymethyl methacrylate, MS resin, AS resin, or polystyrene is dissolved in the syrup can be adopted.

The resin composition of the present invention has impact resistance, elongation,
It has an excellent balance of weather resistance, transparency, heat deformation resistance, etc.
Signage supplies such as transom signboards, rooftop signboards, display supplies such as showcases, dividers, store displays, fluorescent lighting covers, mood lighting covers, lamp shades, light ceilings, light walls, lighting equipment such as chandeliers, pendants, mirrors, etc. Interior parts, doors, dome, safety window glass, partitions, staircase sidings, balcony sidings, construction parts such as roofs for leisure buildings, aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus light shields,
Transportation related parts such as site visors, rear visors, head wings, headlight covers for automobiles, nameplates for audiovisual equipment, stereo covers, TV protective masks, electronic equipment parts such as vending machines, medical equipment such as incubators and X-ray parts Equipment parts, mechanical covers, instrument covers, laboratory equipment, rulers,
Equipment related parts such as dials, observation windows, etc., optical parts such as liquid crystal protection plates and Fresnel lenses, traffic related parts such as road signs, information boards, curved mirrors, soundproof walls, etc., tank parts such as large tanks, box tanks, etc. Sanitary goods such as bathtubs, game parts such as toys, other greenhouses, clock panels, desk mats,
It can be used for various industrial applications such as welding protection masts.

The syrup of the present invention can be used alone, or can be used by blending various additives.
Additives include fibrous reinforcing agents such as glass fibers, carbon fibers, and aramid fibers; inorganic fillers such as calcium carbonate, aluminum hydroxide, silica, mica, monomorillonite, and whiskers; silane-based coupling agents; and titanium-based additives. Interface modifiers such as coupling agents, ultraviolet absorbers, hindered amine light stabilizers, primary antioxidants, polymer stabilizers such as secondary antioxidants, coloring agents such as dyes and pigments,
Polymerization inhibitors, viscosity-imparting agents such as Aerosil, flame retardants,
Release agents and the like. These can be added in combination.

In a preferred embodiment, syrups 99 to 10
1 to 90% by weight of inorganic filler (c) based on% by weight
And a method for radical polymerization.

[0052]

The present invention will be described in more detail with reference to the following examples. In each description, "parts" indicates "parts by weight". The physical properties of the obtained cured product were evaluated according to the following standards. (1) Danestadt impact strength: DIN 53453 (2) Flexural modulus: ASTM D-790 (3) Tensile elongation at break: ASTM D-638 (4) Total light transmittance: ASTM D-542, at 3 mm thickness Measurement. (5) Temperature dependence of haze of molded plate Regarding temperature dependence of haze of molded plate, ASTM D1
The haze at 0 ° C., 23 ° C., and 70 ° C. was measured according to 003 standard. (6) Impact Whitening Property and Bending Whitening Property of Molded Plate The impact whitening property of the molded plate was evaluated by visually observing the appearance of the plate after the falling weight impact test. ASTM D542 for falling weight impact test
0cm (GD) standard, 10cm square flat plate (3mm)
Then, a weight with a load of 1 kg was dropped from a height of 30 cm. The bending whitening property of the formed plate is measured by a bending test (ASTM D-
790) was visually evaluated for the appearance of the molded article.

Reference Example 1 330 g of poly (ε-caprolactone) diol (Placcel 220, molecular weight 2000, manufactured by Daicel Chemical Co., Ltd.) was placed in a 3 L internal reaction vessel equipped with a stirrer, reflux condenser, and dropping funnel. 165 mol) of methyl methacrylate 77 dehydrated and purified by molecular sieve
7 g of dibutyltin dilaurate (hereinafter referred to as “DBT
L "), and after 15 minutes with nitrogen replacement, 8
The temperature was raised to 0 ° C. 37.3 g (0.20 mol) of xylylene diisocyanate (hereinafter abbreviated as “XDI”) and dehydrated and purified methyl methacrylate (hereinafter abbreviated as “MMA”)
After dropping 50 g of the mixed solution under stirring over 45 minutes,
The mixture was heated and stirred for 45 minutes.

Subsequently, methacrylic acid-2-dehydrated and purified
7. Hydroxyethyl (hereinafter abbreviated as "2-HEMA")
A mixed solution of 6 g (0.07 mol) and 50 g of dehydrated and purified MMA was added dropwise over 15 minutes, and the mixture was directly heated and stirred for 45 minutes. When the reaction solution was cooled to room temperature, the viscosity was 10,000c.
A colorless and transparent urethane syrup (1) of about ps (25 ° C.) was obtained. When a small amount of syrup was added to methanol,
A rubber-like insoluble material precipitated. The weight of the precipitated insoluble matter was 31% of the syrup, and its weight average molecular weight was 180,000.

[Reference Example 2] Polypropylene glycol (molecular weight) subjected to dehydration purification in the same reaction vessel as in Reference Example 1
2000) 330 g (0.165 mol) was dissolved in 1400 g of MMA dehydrated and purified by molecular sieve and DB
0.75 g of TL was added, and after 15 minutes with nitrogen replacement, the temperature was raised to 80 ° C. A mixed solution of 37.3 g (0.20 mol) of XDI and 50 g of dehydrated and purified MMA was added dropwise over 15 minutes, and the mixture was heated and stirred for 45 minutes.

Subsequently, dehydrated and purified 2-HEMA 8.6 was used.
g (0.07 mol) and a mixed solution of 50 g of dehydrated and purified MMA were added dropwise over 5 minutes, and the mixture was heated and stirred for 45 minutes. When the reaction solution was cooled to room temperature, the viscosity was 700 cps.
A colorless and transparent urethane syrup (2) of a degree (25 ° C.) was obtained. The weight of the insolubles precipitated in the same manner as in Reference Example 1 was 22% of the syrup, and its weight average molecular weight was 120,000.

Reference Example 3 In the same reaction vessel as in Reference Example 1, poly (ε-caprolactone) diol (Placcel 22
0, molecular weight 2000, manufactured by Daicel Chemical) 300 g (0.15
Mol) and 6 g of poly (ε-caprolactone) triol (Placcel 320, molecular weight 3000, manufactured by Daicel Chemical).
(002 mol) was dissolved in 1300 g of MMA dehydrated and purified by a molecular sieve, 0.75 g of DBTL was added, and after 15 minutes with nitrogen replacement, the temperature was raised to 80 ° C. XDI3
4.6 g (0.184 mol) of MMA50 dehydrated and purified
g of the mixed solution was added dropwise with stirring over 30 minutes, and then the mixture was heated and stirred for 45 minutes.

Subsequently, dehydrated and purified 2-HEMA 8.6 was used.
g (0.07 mol) and a mixed solution of 50 g of dehydrated and purified MMA were added dropwise over 15 minutes, and the mixture was heated and stirred for 45 minutes. When the reaction solution was cooled to room temperature, the viscosity was 100 cp.
A colorless and transparent urethane syrup (3) of about s (25 ° C.) was obtained. The weight of the insolubles precipitated in the same manner as in Reference Example 1 was 22% of the syrup, and the molecular weight between the crosslinking points (theoretical value) was about 60,000.

Reference Example 4 This reference example is disclosed in
It is an additional test of urethane syrup used in Examples 1 to 6 and Comparative Examples 1 to 3 of JP-A-217-217.

591 g (0.30 mol) of poly (ε-caprolactone) diol (Placcel 220, molecular weight 2000, manufactured by Daicel Chemical) was dehydrated in a 5 L content vessel equipped with a stirrer, reflux condenser, and dropping funnel. After dissolving in 3700 g of ordinary unpurified MMA, adding 2.2 g of DBTL and raising the temperature to 70 ° C., 65 g (0.345 mol) of XDI was added dropwise with stirring. Thereafter, the internal temperature is maintained at 80 ° C.
Normal 2-HEMA1 not dehydrated and purified after 60 minutes
1.7 g (0.09 mol) was added, and after a further 60 minutes, the reaction solution was cooled to room temperature.
A colorless and transparent urethane syrup (4) of about 0 cps (25 ° C.) was obtained. The weight of the insoluble material precipitated in the same manner as in Reference Example 1 was 15% of the syrup, and the weight average molecular weight was 60,000.

Example 1 To 60 parts of the urethane syrup (1) obtained in Reference Example 1, 60 parts of MMA was added to dilute the urethane content to 15% by weight, and 2,2′-azobis (2,4′-dimethyl) was added. Valeronitrile) (hereinafter abbreviated as "AIBN") 0.0
6 parts were added, mixed well, and degassed under reduced pressure to obtain a syrup for cast polymerization. The obtained syrup for cast polymerization was placed in a closed glass cell, heated in a water bath at 60 ° C. for 3 hours, then in an air bath at 120 ° C. for 2 hours, and then cooled to obtain a cured product having a thickness of 3 mm. Was. The impact resistance, flexural modulus, tensile elongation, and transparency of the obtained cured product were measured, and the results shown in Table 1 were obtained.

After the obtained cured product was stained with a ruthenium oxide aqueous solution, the specimen was cut and observed with a transmission electron microscope [JEM-100CXII manufactured by JEOL Ltd.]. The cured product is composed of particles of polymethyl methacrylate (0.1 to 1 μm) in a continuous phase derived from polyurethane.
m) formed a dispersed microphase-separated structure.

Example 2 The same procedure as in Example 1 was carried out except that the mixture having a urethane content of 15% by weight
Parts, ethylene glycol dimethacrylate 1.2 parts, and n-octyl mercaptan 0.12 part, and the other conditions were the same as in Example 1 to obtain a syrup for polymerization and a cured product (Table 1). . Continuous phase and dispersed phase (0.1-1
The progress of the phase separation (μm) was more remarkable than that of Example 1.

Example 3 To 90 parts of the urethane syrup (2) obtained in Reference Example 2, 30 parts of MMA was added to dilute the urethane content to 15% by weight. Other conditions are the same as those in Example 1.
A syrup for polymerization and a cured product were obtained in the same manner as described above (Table 1). The progress of the phase separation between the continuous phase and the dispersed phase (0.1 to 1 μm) was almost the same as in Example 1.

Example 4 In Example 3, the urethane syrup (3) obtained in Reference Example 3 was used in place of the urethane syrup (2), and the other conditions were the same as in Example 3 for polymerization. A syrup and a cured product were obtained (Table 1). The progress of the phase separation between the continuous phase and the dispersed phase (0.1 to 1 μm) was less than that in Example 1.

Comparative Example 1 AIBN (0.06 part) was added to 120 parts of the urethane syrup (4) obtained in Reference Example 4 and mixed well, followed by degassing under reduced pressure to obtain a syrup for cast polymerization. . Next, a cured product was obtained in the same manner as in Example 1 (Table 1). The impact resistance and tensile elongation were slightly improved by using low molecular weight modified polyurethane. Although the cured product formed a continuous phase derived from polyurethane, the progress of microphase separation was insufficient.

Comparative Example 2 In Comparative Example 1, 0.06 part of AIBN was added to 120 parts of urethane syrup (4), and 1.2 parts of ethylene glycol dimethacrylate and 0.12 parts of n-octyl mercaptan were further added. Was added. The other conditions were the same as in Comparative Example 1 to obtain a syrup for polymerization and a cured product (Table 1). The impact resistance and tensile elongation were slightly improved by using low molecular weight modified polyurethane. The cured product had a microphase-separated structure, and the degree of phase separation between the continuous phase and the dispersed phase (0.1 to 1 μm) was more remarkable than that of Comparative Example 1.

[Comparative Example 3] AIBN was added to the MMA 120 part.
0.06 parts were added, mixed well, and degassed under reduced pressure to obtain a syrup for cast polymerization. Next, a cured product was obtained in the same manner as in Example 1 (Table 1).

Example 5 Urethane Syrup (1) 10
0 parts of aluminum hydroxide 150 parts and AIBN 0.05
Then, the mixture was sufficiently stirred, and then defoamed under reduced pressure to obtain a syrup for cast polymerization. Next, a cured product was obtained in the same manner as in Example 1 (Table 2). The cured product had a microphase-separated structure, and the degree of phase separation between the continuous phase and the dispersed phase (0.1 to 1 μm) was almost the same as in Example 1.

[Comparative Example 4] 150 parts of aluminum hydroxide and 0.05 parts of AIBN were added to 100 parts of MMA syrup, sufficiently stirred, and degassed under reduced pressure to obtain a syrup for cast polymerization. Next, a cured product was obtained in the same manner as in Example 1 (Table 2). The cured product contains no urethane component,
No phase separation structure was observed.

Example 6 The thickness of 3 m obtained in Example 4
The cured product of m was evaluated for haze temperature dependence, impact whitening property and bending whitening property (Tables 3 and 4). This cured product was cut into a size of 2 m in length and 1 m in width, and fitted into a metal frame for a soundproof wall. When left outdoors in good weather, the surface temperature of the cured product rose to 40 ° C. due to direct sunlight, but without increasing the haze value, a soundproof wall having excellent appearance and impact resistance was obtained.

Comparative Example 5 Acrylite (registered trademark) L [Mitsubishi Rayon Co., Ltd.] which is a general methacrylic resin plate
Manufactured) and a thickness of 3 mm were evaluated (Tables 3 and 4).

[Comparative Example 6] Acrylite (registered trademark) ML (manufactured by Mitsubishi Rayon Co., Ltd.), which is an impact-resistant methacrylic resin plate having a structure in which rubber particles are dispersed in a continuous phase of polyMMA, was 3 mm thick. Used and evaluated (Tables 3 and 4).

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

The resin composition of the present invention has excellent weather resistance, transparency, and heat deformation resistance, and further has high impact resistance and tensile elongation. Molded articles or molded parts made of this resin composition,
Compared to conventional acrylic polymer materials, it can be applied to application fields that require stricter impact resistance, rigidity, elongation, transparency and weather resistance, signage supplies, display supplies, lighting supplies, interior supplies It is useful for construction parts, transportation equipment parts, electronic equipment parts, medical equipment parts, equipment parts, optical parts, transportation parts, aquarium supplies, sanitary supplies, game supplies and the like.

Claims (9)

[Claims] 1. A composition comprising 5 to 50% by weight of a modified polyurethane component (A) and 50 to 95% by weight of an acrylic polymer component (B) containing 50% by weight or more of methyl methacrylate units, It has a microphase-separated structure in which particles of the acrylic polymer component (B) are dispersed in the continuous phase of the component (A), and at least a part of the modified polyurethane component (A) and at least a part of the acrylic polymer component A resin composition obtained by chemically bonding (B). 2. The resin composition according to claim 1, wherein the modified polyurethane component (A) has a weight average molecular weight of 100,000 or more. 3. A modified polyurethane (a) 5 having an alkenyl group at a polymer chain terminal and having a weight average molecular weight of 100,000 or more.
The polyurethane-containing acrylic syrup comprising 50 to 95% by weight of an acrylic monomer (b) containing 50 to 95% by weight and 50% by weight or more of methyl methacrylate is cured by a radical polymerization method. A method for producing a resin composition. 4. The method for producing a resin composition according to claim 3, wherein the modified polyurethane (a) is linear. 5. The modified polyurethane (a) is composed of an aliphatic or aromatic organic diisocyanate and a molecular weight of 500 to 200.
Reaction product of a polyurethane obtained by polyaddition reaction of a polydiol of No. 0 with a compound having at least one active hydrogen atom capable of reacting with an isocyanate group and a radically polymerizable ethylenically unsaturated alkenyl group. The method for producing a resin composition according to claim 4, wherein: 6. The radical polymerization according to claim 3, further comprising adding 1 to 90% by weight of an inorganic filler (c) to 99 to 10% by weight of the polyurethane-containing acrylic syrup. A method for producing a resin composition, comprising: 7. The method according to claim 3, wherein the molecular weight having a plurality of alkenyl groups is 10 to 100 parts by weight of the polyurethane-containing acrylic syrup.
0 to 25 parts by weight of a monomer which is not more than 00, a chain transfer agent 0
A method for producing a resin composition, wherein 1 part by weight is blended to carry out radical polymerization. 8. A molded article or molded part comprising the resin composition according to claim 1 or 2. 9. A molded article or molded part is a signboard article, a display article, a lighting article, an interior article, a building part, a transport-related part, an electronic equipment part, a medical equipment part, an equipment-related part, an optical-related part, a traffic-related part. Parts, aquarium supplies,
The molded article or molded part according to claim 8, which is any one selected from sanitary articles and game articles.