JPH0694495B2 - Polymerizable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable composition capable of obtaining a polymer having excellent mechanical properties, thermal properties, chemical resistance and the like. More specifically, it relates to a polymerizable composition comprising a partial copolymer of an unsaturated carbonate compound and an unsaturated carboxylic acid or an anhydride thereof, and an inorganic filler.

[Conventional technology]

Conventionally, a resin molded product filled with an inorganic powder is used in various fields because it has excellent mechanical properties and flame retardancy as compared with a resin alone molded product. In particular, resin molded products obtained by filling acrylic resin or unsaturated polyester resin with white inorganic powder such as aluminum hydroxide, silica, and calcium carbonate have a wide variety of uses as artificial marble, such as system kitchens and washroom counter wall materials. In recent years, the demand for such resin-molded products is expanding, and their development is also active.

Such a resin molded article uses a polymer of an unsaturated carbonate compound as a matrix and silica or alumina hydrate as an inorganic filler as disclosed in JP-A-61-11935. It has been known.

[Problems to be solved by the invention]

Since the above-mentioned resin molded product has a good appearance and texture, it can be used as an artificial marble, but mechanical strength, scratch resistance, and heat resistance are not sufficiently satisfactory. Its use as a building material in places where strength and heat resistance were required was restricted.

[Means for solving problems]

The present inventors intend to improve mechanical strength, scratch resistance and heat resistance while maintaining the appearance and texture of a resin molded product obtained from the above unsaturated carbonate compound and inorganic filler as an artificial marble. With the aim of As a result, by using a partial copolymer of an unsaturated carbonate compound and an unsaturated carboxylic acid or its anhydride and an inorganic filler, it was found that the resin molded product obtained satisfies the above-mentioned object, and the present invention is completed. Came to let.

That is, the present invention includes (a) the following formula in one molecule: (However, A is an alkenyl group.) A partial copolymer of an unsaturated carbonate compound having two or more unsaturated carbonate groups represented by: and an unsaturated carboxylic acid or an anhydride thereof, and (b) an inorganic filler And a polymerizable composition.

The partial copolymer, which is one component of the polymerizable composition of the present invention,
It is a compound in which an unsaturated carboxylic acid or its anhydride is added to an unsaturated carbonate compound having two or more unsaturated carbonate groups in one molecule. In general, the unsaturated carbonate compounds that are preferably used as a raw material for the partial copolymer in the present invention are as follows.

The following formula [I] In the above general formula, the number of carbon atoms of the alkenyl group represented by R ¹ and R ³ is not particularly limited. However, the number of carbon atoms is preferably in the range of 2 to 4 from the viewpoint of easy polymerization. Specific examples of such an alkenyl group include a vinyl group, an allyl group,
Examples thereof include a methallyl group and a butenyl group. Especially, considering the mechanical strength, scratch resistance and heat resistance of the resin molded product obtained by polymerizing the polymerizable composition of the present invention, the allyl group is most preferable. Further, in the general formula [I], R ²
The carbon number of the alkylene group represented by is not particularly limited, but the carbon number is in the range of 2 to 8, and further 2 to 6 from the viewpoint of mechanical strength, scratch resistance and heat resistance of the obtained resin molded product. It is preferable. For example, ethylene group, trimethylene group, tetramethylene group, propylene group, isobutylene group, neopentylene group and the like can be mentioned. Further, in the general formula [I], n may be an integer of 1 or more, but for the same reason as above, 1 to 20 and more preferably 1 to 10
Is preferably an integer.

The following formula [II] In the above general formula [II], the number of carbon atoms of the alkyl group represented by R ⁴ , R ⁷ and R ⁸ is not particularly limited, but in the range of 1 to 5 in consideration of the scratch resistance of the obtained resin molded product. Is preferred. Further, the aryl group represented by R ⁴ is preferably a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a benzyl group or the like. Further, examples of the substituent of the alkyl group or aryl group represented by R ⁴ include a halogen atom, a nitro group, an alkoxy group and the like. Furthermore, R ⁵ is CH _{2 L} or OCH ₂ CH _2
The group represented by _K is preferable, and among them, R ⁵ is CH _{2
When L} is 1, l is preferably in the range of 0 to 30, and when R ⁵ is OCH ₂ CH _{2 K} , k is preferably in the range of 1 to 20.

Specific examples of unsaturated carbonate compounds that are preferably used in the present invention are as follows. For example, Etc.

The unsaturated carboxylic acid or its anhydride, which is the other raw material of the partial copolymer, is a compound having a vinyl group and a carboxyl group in the molecule, a compound having a vinyl group and two carboxyl groups forming an anhydride. The compounds mentioned can be used without any limitation. Specific examples of unsaturated carboxylic acids or anhydrides thereof that can be preferably used in the present invention include, for example, monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, tiglic acid and cinnamic acid; Maleic acid,
Dibasic acids such as citraconic acid; and dibasic acid anhydrides such as maleic anhydride and citraconic anhydride.

Among these unsaturated carboxylic acids or their anhydrides, considering the mechanical strength, scratch resistance and heat resistance of the resin molded product obtained by polymerizing the polymerizable composition of the present invention, the dibasic acid or its anhydride is taken into consideration. The thing is used preferably.

The composition ratio in the case of performing partial copolymerization of the unsaturated carbonate compound represented by the general formula [I] and the unsaturated carboxylic acid or its anhydride is 100 parts by weight of the unsaturated carbonate compound, unsaturated carboxylic acid, Or its anhydride is 0.01
˜50 parts by weight, preferably 0.1 to 40 parts by weight.

The partial copolymer used in the present invention is a liquid prepolymer obtained by preliminarily polymerizing the unsaturated carbonate compound and the monomer mixture of the unsaturated carboxylic acid or the anhydride thereof to increase the viscosity of the mixture. Incidentally, such a copolymer is
It can be stored for a long period of time and is effective in suppressing crystal precipitation and gelation.

In the present invention, it is desirable that the partial copolymer generally has a viscosity of 15 to 1000 centipoise at 25 ° C., further 20 to 300 centipoise, in order to facilitate operability during molding. Therefore, the amount of radical initiator used is 15 to 1000 centipoise (25
It is preferably determined to have a viscosity of (° C.). Generally, 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight of a radical polymerization initiator is used per 100 parts by weight of the unsaturated carbonate compound and a monomer mixture of the unsaturated carboxylic acid or its anhydride. Is desirable. Known radical initiators are used in the production of the partial copolymer, and typical examples thereof include azo compounds such as azobisisobutyronitrile;
Organic peroxides such as ketone peroxide, diacyl peroxide, dialkyl peroxide, hydroperoxide, and perester can be preferably used. Also,
In the production of the partial copolymer, the reaction temperature depends on the type of the radical polymerization initiator used, but is generally 50 to 150 ° C. to prevent the partial copolymer from coloring and increasing the viscosity during storage.
Is preferred.

The above partial copolymer can be produced by polymerizing the monomer mixture in an inert solvent and then removing the solvent.

As the inorganic filler which is the other component of the polymerizable composition of the present invention, known ones which are generally used as fillers for synthetic resins are used without any limitation. For example, aluminum compounds such as alumina and aluminum hydroxide;
Magnesium compounds such as magnesium oxide, magnesium hydroxide and magnesium carbonate; calcium compounds such as calcium carbonate and calcium sulfate; silicon compounds such as silica and quartz; glass powder; natural stone powder and the like. Among these inorganic fillers, the use of hydroxide is particularly preferable from the viewpoint of improving heat resistance.

The particle size of the inorganic filler is preferably in the range of 5 to 30 μ from the viewpoint of filling properties, slurry operability after filling, and the like, and the shape thereof is generally spherical, or a shape close to spherical can be particularly preferably used. .

The composition ratio of each component of the polymerizable composition of the present invention described above is not particularly limited and can be selected from a wide range. However, it is generally desirable to add 1 to 1000 parts by weight, preferably 10 to 500 parts by weight, of the inorganic filler to 100 parts by weight of the partial copolymer.

The polymerizable composition of the present invention can be easily initiated by heat or light, but it is generally preferable that the polymerizable composition is heated by a radical polymerization initiator. Known ones are used as the radical polymerization initiator,
Typical examples include azo compounds such as azobisisobutyronitrile; organic peroxides such as ketone peroxide, diacyl peroxide, dialkyl peroxide, hydroperoxide, and perester. It The amount of the polymerization initiator used varies depending on the type of partial copolymer, polymerization conditions, etc., but is generally 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the partial copolymer. Is desirable. Furthermore, a means such as addition of a surfactant or an inorganic salt such as sodium dodecylbenzene sulfonate, or addition of an adhesive component such as a silane coupling agent is necessary in order to assist the dispersion of the polymerization reaction system during the polymerization. It can be adopted according to.

Regarding the polymerization conditions, the type and amount of the partial copolymer used, and the type and amount of the radical initiator vary, but generally 20 to 150 ° C., 0.5 to 40 hours, preferably 40 to
130 ° C, 1 to 20 hours is desirable.

As a method for molding the polymerizable composition in the present invention, a predetermined amount of the above radical initiator is added to the polymerizable composition, and the mixture is kneaded in the air or an inert gas atmosphere as necessary, and vacuum degassing is performed. After degassing using the method described above, a known cast polymerization method of injecting into a mold and heat curing, or a compression molding method of compressing a similarly degassed polymerizable composition and heat curing, etc. should be adopted. You can With respect to this molding, if the viscosity of the polymerizable composition is extremely low, the inorganic filler may be precipitated during molding, resulting in non-uniform composition of the resulting molded body. In such a case, by increasing the polymerization degree of the partial copolymer which is one component of the polymer composition in the present invention to increase the viscosity, the polymer composition is increased in viscosity and A method that prevents settling is desirable. In order to facilitate the preparation of the degree of polymerization of the partial copolymer, it is preferable to use an unsaturated carbonate compound having an allyl carbonate group as the unsaturated carbonate group.

Of course, in the polymerization of the polymerizable composition of the present invention, various stabilizers and additives such as a release agent, an ultraviolet absorber, an antioxidant, a pigment antistatic agent, etc. are selected and used as necessary. be able to.

(Effect) The polymerizable composition of the present invention gives a polymer having improved mechanical strength, scratch resistance and heat resistance by adding an unsaturated carboxylic acid or an anhydride thereof. Moreover, the appearance and texture of the polymer are not impaired at all by the addition of unsaturated carboxylic acids or their anhydrides. Further, the obtained polymer has excellent chemical resistance. Therefore, the resin molded product obtained by polymerizing the polymerizable composition of the present invention can be widely used for applications as an artificial marble, and particularly, mechanical strength,
It can be suitably used as a building material for places where scratch resistance, heat resistance and chemical resistance are required.

(Examples) In order to describe the present invention more specifically, the following examples will be given, but the present invention is not limited to these examples.

The physical properties of the molded products obtained in the examples were measured by the following test methods.

Method for Measuring Physical Properties of Molded Body (1) Appearance The molded body polymerized and molded under each condition was visually observed from right above under white light.

(2) Hardness The hardness was measured based on the ASTM D-785 test method. (L-scale) (3) Izod impact strength Measured based on the ASTM D-256 test method. (With V notch) (4) Chemical resistance Acetone, benzene, toluene, carbon tetrachloride, chloroform, trichlene, methanol, ethanol, acetic acid 10%, N, N-dimethylformamide, dimethylsulfoxide, 1 on each molded product surface , 4-dioxane, hydrogen peroxide 10
%, Sulfuric acid 10%, hydrochloric acid 10%, sodium hydroxide 10%, sodium carbonate 20% were added dropwise, and the mixture was allowed to stand at room temperature for 24 hours in an open system. Then, the adhered surface was washed with a neutral detergent, wiped with a dry, clean gauze, and allowed to stand for 1 hour. Then, the presence or absence of a surface change was visually observed from right above under white light.

(5) Heat resistance The heat distortion temperature was measured based on the ASTM D-648 test method.

(5) Scratch resistance A scratch resistance tester manufactured by Fukuda Machine Industry Co., Ltd. was attached with # ○○○○ steel wool, and the surface of each molded body was reciprocated 10 times under a load of 1 kg. The degree of scratches was visually observed, and a state in which no damage was observed was A, and the degree of scratches of the methacrylate polymer was E, and five-level evaluation from A to E was performed.

Example 1 Diethylene glycol bisallyl carbonate represented by the following formula (hereinafter abbreviated as ADC), A weight ratio of maleic anhydride of 100/1, a composition of a partial copolymer having a viscosity of 50 centipoise and aluminum hydroxide in a weight ratio of 40/60 to a polymerizable composition, diisopropyl peroxy as a radical polymerization initiator. 3 parts by weight of dicarbonate was added to 100 parts by weight of the copolymer and mixed well. After degassing this composition, pour it into a glass mold consisting of two sheets of glass and a gasket, and keep it at 40 ° C to 90 ° C.
After polymerizing while raising the temperature in 20 hours, the mold is released and the size is 40
A molded plate of 0 × 400 × 3 mm was obtained. The obtained molded product was white and exhibited remarkably good properties in hardness, chemical resistance and heat distortion temperature. The results are shown in Table 1.

Examples 2 to 15 Partial copolymers of various unsaturated carbonate compounds and unsaturated carboxylic acids or their anhydrides shown in Table 1 in place of the partial copolymers and inorganic fillers used in Example 1 and Using various inorganic fillers, molding was performed under the polymerization conditions shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 and 2 Experimental Examples 1 and 2 except that a partial copolymer of an unsaturated carbonate compound and an unsaturated carboxylic acid or an anhydride thereof in Examples 1 and 2 was replaced with a partial polymer of an unsaturated carbonate compound. It was carried out in the same manner as in 2, and the results are shown in Table 1.

Claims (1)

[Claims] 1. A compound represented by the following formula in one molecule: (However, A is an alkenyl group.) A partial copolymer of an unsaturated carbonate compound having two or more unsaturated carbonate groups represented by: and an unsaturated carboxylic acid or an anhydride thereof, and (b) an inorganic filler A polymerizable composition comprising: