WO2001098429A1

WO2001098429A1 - Thickening agent, thickening composition and process for producing the same, sheet molding compound or bulk molding compound and process for producing the same, and molded resin and process for producing the same

Info

Publication number: WO2001098429A1
Application number: PCT/JP2001/005351
Authority: WO
Inventors: Seiya Koyanagi; Katsumi Yonekura; Yuichiro Kishimoto; Akitada Yanase; Yuuji Kazehaya
Original assignee: Mitsubishi Rayon Co., Ltd.
Priority date: 2000-06-22
Filing date: 2001-06-22
Publication date: 2001-12-27

Abstract

A thickening agent which comprises an inorganic filler (F) and a syrup (S) comprising a polymer having functional groups reactive with the inorganic filler (F); a sheet molding compound (SMC) or bulk molding compound (BMC) which each contains an inorganic filler (F) containing the oxide or hydroxide of a divalent metal and a syrup (S) comprising a polymer having functional groups reactive with the inorganic filler (F), the amount of the oxide or hydroxide being 0.6 wt.% or smaller based on the whole syrup (S); a process for producing a molded resin which comprises curing the SMC or BMC with heating and pressing; and a thickening composition characterized by containing a compound (A) having two or more acid groups per molecule and a compound (B) having two or more basic groups per molecule.

Description

Specification

增 Thickener, thickening composition, its manufacturing method, sheet molding

'' Compound or bulk molding compounds and

Technical Field of the Invention

The present invention relates to a thickener, a thickening composition and a method for producing the same, a sheet molding compound (hereinafter abbreviated as SMC) or a bulk molding compound (hereinafter abbreviated as BMC) and a method for producing the same, and SMC or BMC. It relates to the resin molding used. Background art

Acryl-based resin molded products containing an acrylic resin mixed with an inorganic filler such as aluminum hydroxide have various outstanding functional characteristics such as excellent molded appearance such as depth (transparency) and gloss. It is widely used as artificial marble in counters such as kitchen counters, vanities, waterproof pans, building materials, and other uses.

As a method for producing this acryl-based resin molded article, a premix of an acryl-based monomer or an acryl-based syrup in which an inorganic filler is dispersed is thickened with a thickener to form an acryl-based SMC or BMC. After that, a method of obtaining an acryl-based resin molded product by heating and curing under pressure has been conventionally performed. In order to increase the mechanical strength of these ataryl resin molded products, it is common to add a fiber reinforcing agent such as glass fiber.

For example, Japanese Patent Publication No. 64-111652 discloses a premix consisting of an acrylic syrup containing a polymer having a carboxyl group, an inorganic filler and glass fibers, and magnesium oxide or water as a thickener. Acryl-based SMC that uses a chemical reaction between a carboxyl group and a divalent metal oxide or hydroxide using a divalent metal oxide or hydroxide such as calcium oxide In addition, an acryl-based resin molded product obtained by heating and curing this acryl-based SMC is disclosed. However, resin molded products obtained by molding acryl-based SMC described in Japanese Patent Publication No. 64-111652 are handled as SMC or BMC! Since the divalent metal oxide or hydroxide of the viscosity agent is in the form of fine powder, it easily aggregates, and the divalent metal oxide or hydroxide precipitates on the obtained molded product surface There was a problem of shaking. In addition, divalent metal oxides or hydroxides used as thickeners have high water absorption and are in the form of fine powder, so they are susceptible to moisture, and depending on the use environment, may have a sufficient increase. There is a problem that the viscosity cannot be obtained and the handling as SMC or BMC becomes poor. Furthermore, since divalent metal oxides or hydroxides are strong and water-absorbing, when hot molded articles are tested for hot water, divalent metal oxides or hydroxides precipitate on the molding surface. However, they have the drawback that they appear as protrusions and blisters and their appearance is significantly impaired. For this reason, improvements are required for applications requiring water resistance, such as kitchen applications, bath applications, and water tank applications.

In order to improve the water resistance, studies have been made to increase the viscosity without using a divalent metal oxide or hydroxide. For example, Japanese Patent Publication No. 114650/1993 discloses an acrylic SMC or BMC that is made thicker by utilizing a urethanation chemical reaction between an isocyanate group and a hydroxyl group. In addition, for example, Japanese Patent Application Laid-Open No. 6-287394 discloses an ataryl-based BMC thickened by utilizing a stereocomplex forming reaction between an isotactic polymer and a syndiotactic polymer. . Further, for example, Japanese Patent Application Laid-Open No. 10-67906 discloses an acrylic BMC whose viscosity is increased by physically dissolving a polymer powder. However, the acryl-based SMC or BMC described in Japanese Patent Publication No. 1-46503 is susceptible to rash because of the use of an isocyanate compound, and has a problem in handling. In addition, in the method described in JP-A-6-2877394, in order to produce an isotactic polymer, it is necessary to carry out polymerization at a temperature of minus several tens of degrees or less using a Grignard / reagent. The range of manufacturing conditions is extremely narrow, and it is difficult to manufacture industrially efficiently. Also, Japanese Patent Application Laid-Open No. H10-69906 describes that a fiber reinforcing agent such as glass fiber or carbon fiber can be added. High content exceeding 10% by mass If it is contained at a ratio, the fluidity of the compound during molding becomes poor. As a result, (1) the molded product becomes underfilled, or the glass fiber comes out on the surface of the molded product, resulting in poor appearance. (2) Since the glass fiber is hardly oriented at the time of molding, the obtained molded product is designed. It tends to be lower than usual, with only mechanical strength.

In addition, since SMC described in Japanese Patent Publication No. 641-11652 uses an acryl resin as a resin component, an acrylic resin molded product obtained by heating and curing the resin is: Good weather resistance compared to unsaturated polyester resin molded products. For example, as described in the same gazette, the unsaturated polyester resin molded product shows no choking, discoloration, and decrease in gloss even after a 500-hour accelerated exposure test using a sunshine analyzer. On the other hand, the acrylic resin molded article shows almost no chalking, discoloration, and decrease in gloss.

However, although the acrylic resin molded product described in Japanese Patent Publication No. 64-111652 has better weather resistance than the unsaturated polyester resin molded product as described above, it is actually used for outdoor applications. Weather resistance is still insufficient for use in Specifically, for example, an acrylic resin molded product described in Japanese Patent Publication No. 6-116162 is used to convert a water tank panel, an outer wall panel, a container panel, a solar cell panel, and a car exterior. Panel, signal box, transformer box, parabolic antenna, radar dome, ridge bridge shield, bench, park play equipment, pool play equipment, manhole cover, water meter cover, railway cable ^^ REIT, sash window frame, When used for outdoor applications such as doors, fences, outboard motor covers, corrugated boards, etc., gloss reduction, discoloration, embossing of glass fiber, etc., occurred, and this was not practical.

Thus, it can be seen that practical weatherability of materials used for outdoor applications cannot be predicted by a 500-hour accelerated exposure test.

In fact, weathering tests for materials used in outdoor applications need to be judged based on the results of accelerated exposure tests for a longer time, for example, 150 hours. For example, if the accelerated exposure test of an acrylic resin molded product described in Japanese Patent Publication No. 64-111652 is continued for a long time up to 1500 hours, chalking does not occur, but gloss reduction, In addition to causing deterioration of the acryl-based resin itself such as discoloration, the interface between the glass fiber and the acryl-based resin is deteriorated, and the glass fiber is raised. Disclosure of the invention

An object of the present invention is to provide a thickener, a viscous composition, SMC or BMC, which can provide a resin molded product having excellent handleability and excellent water resistance, and a method for producing the same. In particular, it is an object of the present invention to provide a method for producing a resin molded article having excellent water resistance, particularly excellent hot water resistance.

Further, an object of the present invention is to provide an SMC or BMC containing a fiber reinforcing agent, the SMC or the BMC having good moldability, and a molded appearance using the SMC or the BMC. To provide a molded article having good mechanical strength. Further, an object of the present invention is to provide an SMC or BMC capable of obtaining a resin molded product usable for outdoor use as described above even when a fiber reinforcing agent such as glass fiber is contained, And to provide a resin molded product obtained by curing the same and having excellent weather resistance.

The present inventors have studied to achieve the above object, and as a result, by using a syrup containing a polymer having a functional group that reacts with an inorganic filler, it is possible to use an oxide or hydroxide of a divalent metal. It can be handled without using a thickener, or when using a divalent metal oxide or hydroxide in an extremely small amount! And found that a resin molded product having excellent water resistance can be obtained as a result.

Further, by using a thickening composition containing a compound (A) containing two or more acidic groups in one molecule and a compound (B) containing two or more basic groups in one molecule. It was found that even without using a thickener such as an oxide or hydroxide of a divalent metal, it was possible to increase the viscosity to a state in which handleability was good, and as a result, resin molding with excellent water resistance was found. Find that you can get the goods,

In addition, by setting the parameter I (T) described later to 0.01 or more, it is possible to obtain SMC or BMC having good compound fluidity during molding even when a fiber reinforcing agent is contained. And found that by heating and press hardening this SMC or BMC, a molded product with high productivity, good molded appearance and high mechanical strength can be obtained.

In addition, by expressing a specific complex viscosity, it is In this case, we found that SMC or BMC with good flowability during molding could be obtained, and by heating and curing this SMC or BMC under heat and pressure, high productivity, good molded appearance and good mechanical appearance were obtained. It is found that a molded article with high mechanical strength can be obtained, and by setting parameter J described later to 0.1 or more, a resin having excellent weather resistance even when a fiber reinforcing agent such as glass fiber is contained. It is found that molded products can be obtained, and by combining UV absorbers and light stabilizers in SMC or BMC, resin molded products that can be sufficiently used for outdoor applications can be obtained with high productivity. I found that.

That is, the present invention provides a thickener comprising an inorganic filler (F) and a syrup (S) containing a polymer having a functional group which reacts with the inorganic filler (F);

0.6 mass of divalent metal oxide or hydroxide based on the total amount of syrup (S). / ₀ or less, and a syrup (S) containing a polymer having a functional group that reacts with the inorganic filler (F). SMC or BMC, which may contain a textured material (W);

An inorganic filler (F), and a polymer having a functional group that reacts with the inorganic filler (F), wherein the content of the divalent metal oxide or hydroxide is 0.6% by mass or less. A method for producing SMC or BMC, in which a certain syrup (S) is stirred and mixed, and then aged and thickened;

And a method for producing a resin molded product obtained by heating and curing the SMC or BMC;

A thickening composition comprising a compound (A) containing two or more acidic groups in one molecule and a compound (B) containing two or more basic groups in one molecule;

It contains a compound (A) containing two or more acidic groups in one molecule, a compound (B) containing two or more basic groups in one molecule, and an inorganic filler (F). S MC or BMC;

Viscosity obtained by mixing compound (A) containing two or more acidic groups in one molecule with compound (B) containing two or more basic groups in one molecule, then aging and thickening A method for producing the composition;

Compound (A) containing two or more acidic groups in one molecule and two basic groups in one molecule A method for producing BMC, comprising mixing a compound (B) containing at least one and an inorganic filler (F), then aging and thickening;

Compounds having two or more acidic groups in one molecule (A) and a basic group ^2. Or more compounds containing in the molecule (B), and by mixing the inorganic filler (F), the mixture For producing SMC by impregnating with fiber reinforcement (Y) and then aging and thickening; and a method for producing a resin molded product by heating and curing the viscous composition, SMC or BMC. ;

A resin composition (X) comprising a monomer (m), a polymer (p), an inorganic filler (F), and, if desired, a grain pattern material (W), a fiber reinforcing agent (Y), and a curing agent In the SMC or BMC having (Z) as a component, the parameter I (T) represented by the following formula (1) is not less than 0.01 at an arbitrary temperature T within the range of 20 to 80 ° C. Some SMC or BMC;

And a method for producing a resin molded product by curing the SMC or BMC under heat and pressure,

I (T) = t a η δ (Τ) -0.000 2 1 Τ- 0.096 2… (1)

(In the formula, tan S (T) is a loss tangent at a temperature T of the resin composition (X), and a temperature Τ is a degree Celsius.);

A resin composition (X) comprising a monomer (m), a polymer (p), an inorganic filler (F), and, if desired, a grain pattern material (W), a fiber reinforcing agent (Y), and a curing agent in SMC or BMC which a constituent component (Z), the complex viscosity of the resin composition (X) is 3 0 ^{l X 1 0 3 P a ·} s~l X 1 0 7 P a · s of | g囲内SMC or BMC whose complex viscosity at δ 0 ° C is less than 0.2 times the complex viscosity at 30 ° C;

And a method for producing a resin molded product obtained by curing the SMC or BMC by heating and pressure;

SMC or BMC containing monomer (m), polymer (p), inorganic filler (F), fiber reinforcing agent (Y), ultraviolet absorber (U), and light stabilizer (L);

A resin molded product containing an inorganic filler (F) and a fiber reinforcing agent (Y). The condition is that the black panel temperature is 63 ° C and the rainfall is 12 minutes out of 60 minutes using a sunshine analyzer. After the accelerated exposure test for 1 500 hours under A resin molded product characterized by being at least 70 ° / o and having a parameter J represented by the following formula (2) of at least 0.1:

J = 26-0.276 L * -AE * _ab (2)

(In the formula, L * is the lightness index of the molded article before the test, and AE * _ab is the color difference between the molded article before and after the test.);

It is. BEST MODE FOR CARRYING OUT THE INVENTION

The thickener of the present invention comprises a syrup (S) containing an inorganic filler (F) and a polymer having a functional group that reacts with the inorganic filler (F).

The inorganic filler (F) has a function of imparting mechanical strength and heat resistance to the obtained molded article. When a syrup (S) containing a polymer having a functional group that reacts with the filler (F) is used, it has an effect as one component of the thickener.

The inorganic filler (F) is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, silica, fused silica, calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, magnesium oxide, and oxide. Calcium, aluminum oxide, calcium phosphate, talc, myriki, clay, glass powder, and the like can be used, and two or more of these can be used in combination. In particular, when the SMC or BMC of the present invention is used as a molding material for a resin molded product, it is preferable to use aluminum hydroxide, calcium carbonate, silica, fused silica, or glass powder as a main component as an inorganic filler. . Of these, aluminum hydroxide, carbonated calcium carbonate, and magnesium carbonate are more preferred from the aspect of processing of the molded article, and calcium carbonate and magnesium carbonate are particularly preferred from the aspect of thickening control, as described later. Calcium carbonate is most preferred from the viewpoint of the aspect. The calcium carbonate is not particularly limited, and heavy calcium carbonate and light calcium carbonate can be used.

In the thickener of the present invention, the inorganic filler (F) is used as one component of the thickener In this case, the reactivity with the functional group in the component (s) is important.

Specific examples of the inorganic filler (F) having a function as one component of the thickener include, for example, trivalent hydroxides such as aluminum hydroxide, aluminum oxide and the like. Examples include trivalent oxides, divalent hydroxides such as magnesium hydroxide and calcium hydroxide, divalent oxides such as magnesium oxide and calcium oxide, and divalent carbonates such as calcium carbonate and magnesium carbonate. Can be

Of these, divalent carbonates such as calcium carbonate and magnesium carbonate are most preferable because the viscosity can be easily controlled. For example, as calcium carbonate, heavy calcium carbonate and light calcium carbonate can be used, but light calcium carbonate tends to have higher activity than heavy calcium carbonate. Therefore, depending on the type of functional group in the (S) component used, either one of calcium carbonate or a combination of both is used, and the viscosity is increased (增 viscosity) by selecting as appropriate. It is preferable to control the speed and final viscosity). / ,.

Also, among these, trivalent hydroxides such as aluminum hydroxide have high hygroscopicity and therefore contain water, and this water has an effect on the viscosity increase, and it is difficult to control the viscosity increase. It is in.

The amount of the divalent metal oxide or hydroxide is not particularly limited, but if water resistance is required, use it in a range not exceeding 0.6% by mass based on the total amount of the (S) component. Is preferred. If the content of divalent metal oxides or hydroxides exceeds 0.6% by mass based on the total amount of syrup (S), the surface of the molded article after hot water resistance test is Precipitation of oxides or hydroxides of the multivalent metal becomes remarkable, appears as protrusions and blisters, and the appearance tends to be significantly impaired. The content of the divalent metal oxide or hydroxide is preferably 0.5% by mass or less, more preferably 0.3% by mass, based on the total amount of syrup (S). / 6 or less, more preferably 0.25 mass. / ₀ or less is particularly preferable, and it is most preferable that it is not added.

The content of the component (F) is not particularly limited, but is 10% by mass to 80% by mass in the total amount of the SMC or BMC of the present invention. The range of / ₀ is preferred. This is because, when the amount of the component (F) used is 10% by mass or more, the obtained molded article tends to have good mechanical strength and heat resistance and a low linear shrinkage. 0 mass% This is because by setting the content as follows, it becomes possible to impart good gloss to the molded article. (F) The lower limit of the content of the component is 15 mass. / ₀ or more is more preferable, and 20% by mass or more is particularly preferable. The upper limit is 70 mass. /. The following is more preferred, and the content is particularly preferably 60% by mass or less.

The component (S) used in the present invention is a syrup containing a polymer (RP) having a functional group that reacts with the inorganic filler (F), and comprises a polymer (P) and a monomer (m). . This polymer (P) contains a polymer (Rp) having a functional group that reacts with the inorganic filler (F).

In the present invention, the syrup (S) itself contains the polymer (Rp) having a functional group that reacts with the inorganic filler (F) so that the syrup (S) itself and the inorganic filler (F) are mixed. It reacts to develop a viscous effect. Therefore, even if a divalent metal oxide or hydroxide is not used as in the prior art, or even if a very small amount of a divalent metal oxide or hydroxide is used, good handling properties can be obtained. It is possible to thicken to a high viscosity.

In addition, in the present invention, by including a polymer (Rp) having a functional group that reacts with the inorganic filler (F) in the syrup (S), the affinity with the inorganic filler (F) is improved. The dispersion of the inorganic filler (F) is improved. Furthermore, since the bond between the resin component and the inorganic filler interface becomes stronger, the resulting molded article has excellent water resistance, especially hot water resistance.

In the present invention, the polymer (Rp) having a functional group that reacts with the inorganic filler (F) contained in the component (S) refers to a functional group that reacts with the inorganic filler (F) in the polymer molecular chain. Is a polymer containing at least one. The functional group that reacts with the inorganic filler (F) is a functional group that interacts with the inorganic filler (F) through a chemical bond such as a covalent bond, an ionic bond, or a hydrogen bond. Specific examples include a carboxyl group, a phosphoric acid group, a sulfonic acid group, an amino group, an amide group, a glycidyl group, a silanol group, and the like. Among these, a carboxyl group having high reactivity with the inorganic filler (F) is preferable.

The polymer (Rp) having a functional group that reacts with the inorganic filler (F) is not particularly limited as long as it contains one or more of the above-described functional groups in the polymer molecular chain. Sensuality It may have a group, may have a functional group at a molecular chain terminal, or may have a functional group at both of them. In particular, it is preferable that the side chain has a functional group from the viewpoint of thickening. For example, a polymer such as a polyester polymer having the above-described functional group, a butyl polymer having the above-described functional group, and a vinyl ester polymer having the above-described functional group may be used.

The method for producing the polymer (R p) having a functional group that reacts with the inorganic filler (F) is not particularly limited, and examples thereof include a monomer having a functional group that reacts with the inorganic filler (F) described above. (Rm).

The monomer (R m) is not particularly limited, but includes, for example, (meth) acrylic acid, 2- (meth) acryloyloxyxethyl succinic acid, 2- (meth) atalyloyloxicetyl phthalic acid, 211 (Meth) acryloyloxyshethylhexahydrophtalic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monoalkyl / leestenolate fumarate, monoalkylesterole maleate, monoalkylester itaconate, citraconic acid Vinyl monomers containing a hydroxyl group such as monoalkylester; vinyl containing hydroxyl groups such as hydroxyxethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Monomer and e.g. phthalic anhydride, methyltetrahydrophthalic anhydride, A vinyl monomer containing a carboxyl group obtained by an addition reaction with an acid anhydride such as nadic acid; mono (2- (meth) acryloyloxyshethyl) acid phosphate, etc. Bul monomer containing a sulfonic acid group; N, N-dimethinoleaminoethyl (meta) acrylate, N, N-getylaminoethyl / meth Vinyl monomers containing amide groups such as acrylates; vinyl monomers containing amide groups such as (meth) acrylic acid amides; vinyl monomers containing glycidyl groups such as dalicidyl (meth) acrylate Γ- (meth) acryloylpropyltrimethyoxysilane and the like, and a vinyl monomer which becomes a silanol group. These may be used alone or in combination of two or more as necessary. In this specification, “(meth) acryl” means “acryl and / or methacryl”.

Further, the polymer (ρ) is a monomer (R) having a functional group that reacts with the inorganic filler (F). m) may be produced by copolymerizing a bullet type single ft body (Nm) having no functional group which reacts with the inorganic filler (F). The monomer (Nm) having no functional group that reacts with the inorganic filler (F) is not particularly limited. Examples thereof include methyl (meth) acrylate, an alkyl group having 2 to 20 carbon atoms. Alkyl (meth) acrylate having a hydroxyalkyl group having 1 to 20 carbon atoms, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) ) Monoacrylic monofunctional monomers such as acrylates and glycidyl methacrylate; aromatic vinyl monofunctional monomers such as styrene and α-methylstyrene; butyl acetate; and butyl chloride. Can be

Examples of the method for producing the polymer (Rp) include the following methods (1) and (2).

(1) When the polymer (Rp) is a polyester polymer, dicarboxylic acid can be used as a monomer (Rm) having a functional group that reacts with the inorganic filler (F), and dicarboxylic acid and divalent acid can be used. A polyester polymer having a carboxyl group at a terminal is produced by condensation polymerization of alcohol.

(2) When the polymer (Rp) is a bullet-based polymer, the monomer (Rm) having a functional group that reacts with the inorganic filler (F) is a functional group that reacts with the inorganic filler (F). A vinyl monomer having at least a part of a vinyl monomer having a functional group which reacts with the inorganic filler (F) can be used. Manufactured by

The polymer (Rp) used in the present invention is preferably a vinyl polymer, and particularly preferably an acrylic polymer. Therefore, as the monomer (m) used for the production of the polymer (Rp), it is preferable that the main component of the component (Rm) Z or the component (Nm) be an acrylic monomer. It is particularly preferable that the main components of the (Rm) component and the (Nm) component be acryl-based monomers.

The content of the functional group in the polymer (Rp) having a functional group which reacts with the inorganic filler (F) in the component (S) is preferably 0.01 mol or more in the polymer (Rp) l OOOg. When the content is 0.01 mol or more, the reactivity between the (Rp) component and the inorganic filler (F) is improved, and SMC or BMC is handled! Tend to be able to. The upper limit of the content is not particularly limited, but is preferably 3 mol or less. When the content is 3 mol or less, the viscosity of the syrup (S) decreases, and the impregnation into the fiber reinforcing material (Y) tends to be improved. The lower Pt value of this content is more preferably at least 0.03 mol, particularly preferably at least 0.1 mol. The upper limit is preferably 2 mol or less, more preferably 1.5 mol or less.

The weight average molecular weight of the polymer (Rp) having a functional group that reacts with the inorganic filler (F) is not particularly limited, but is preferably from 5,000 to 800,000. When the weight average molecular weight is 5,000 or more, the ultimate viscosity increases, and there is a tendency that SMC or BMC can be thickened to a viscosity with good handleability. The viscosity tends to decrease, and the impregnation into the fiber reinforcement (Y) tends to be good. The lower limit of the weight average molecular weight is more preferably 10,000 or more, and particularly preferably 20,000 or more. The upper limit is more preferably 700,000 or less, and particularly preferably 600,000 or less. The content of the polymer (Rp) having a functional group that reacts with the inorganic filler (F) in the syrup (S) is not particularly limited, but is preferably 3% by mass to 40% by mass based on the total amount of the syrup (S). . When the content is 3% by mass or more, the reactivity with the inorganic filler (F) increases, and the viscosity of SMC or BMC tends to be increased to a good viscosity for easy handling. In addition, the viscosity of the syrup (S) tends to decrease, and the impregnation into the fiber reinforcement (Y) tends to be good. The lower limit of this content is more preferably 4% by mass or more, and 5% by mass. /. The above is particularly preferred. The upper limit is more preferably 35% by mass or less, and particularly preferably 30% by mass or less.

Syrup (S) contains not only polymer (Rp) having a functional group reactive with inorganic filler (F) but also polymer (Np) having no functional group reactive with inorganic filler (F). You may. Examples of the polymer (Np) include a polyester polymer having no functional group that reacts with the inorganic filler (F) and a butyl polymer having no functional group that reacts with the inorganic filler (F). And a polymer such as a belle estenol polymer having no functional group which reacts with the inorganic filler (F).

Next, the monomer (m) constituting the syrup (S) of the present invention will be described. The monomer (m) is not particularly limited, and includes a monomer that undergoes condensation, a monomer that undergoes addition polymerization, a monomer that undergoes ring-opening polymerization, and among others, a butyl monomer that undergoes addition polymerization But preferable.

The content of the monomer (m) in the syrup (S) is not particularly limited, but is preferably 20% by mass to 98% by mass based on the total amount of the syrup (S). When the content is 20% by mass or more, the viscosity of the syrup (S) tends to decrease, and the impregnation into the fiber reinforcing material (Y) tends to be good. It tends to be lower. The lower limit of the content is more preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit is more preferably 95% by mass or less, and particularly preferably 93% by mass or less.

In the SMC or BMC of the present invention, the content of syrup (S) is not particularly limited, but the workability of SMC or BMC and the mechanical strength of a resin molded product obtained from SMC or BMC as a raw material Taking into account the physical properties such as, 5 to 50 mass in the total amount of SMC or BMC. /. Is preferable. This means that the content of the (S) component is 5 mass. By setting the ratio to / ₀ or more, the viscosity of SMC or BMC becomes low, the handleability becomes good, and the content of the component (S) is 50 mass. This is because the ratio of / ₀ or less tends to reduce the shrinkage ratio during curing. The lower limit of the content of the component (S) is more preferably 10% by mass or more, and is 12% by mass. /. The above is particularly preferred. The upper limit is more preferably 45% by mass or less, and particularly preferably 40% by mass or less.

The method for producing the syrup (S) containing a polymer having a functional group that reacts with the inorganic filler is not particularly limited, but a monomer (Rm) having a functional group that reacts with the inorganic filler (F) is used. ) May be used in which the polymer (Rp) is formed in the monomer (Rm) by partial polymerization in advance, or separately, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, A polymer obtained by dissolving a polymer (Rp) having a functional group that reacts with the inorganic filler (F) obtained by a known polymerization method such as dispersion polymerization in a butyl monomer may be used.

The thickening composition of the present invention comprises a compound (A) containing two or more acidic groups in one molecule and a compound (B) containing two or more basic groups in one molecule as constituent components. is there. In the present invention, the compound (A) and the compound (B) are reacted by an acid-base reaction to exhibit a thickening action. Therefore, the divalent metal acid It is possible to increase the viscosity to a good level of handleability without using a compound or hydroxide.

When the component (A) is a compound containing two or more acidic groups in one molecule, it reacts with the component (B) to increase the viscosity of the entire system. The acidic group is not particularly limited, and examples thereof include a carboxyl group, a phosphate group, and a sulfonic group. Of these, a carboxyl group is preferred from the viewpoint of reactivity with the component (B).

(A) The molecular weight of the component is not particularly limited. It may be a low molecular weight compound (A m) having a molecular weight of less than 1000 or a high molecular weight compound (A p) having a molecular weight of 100 or more, but the component (A) and (B) At least one of the components is preferably a compound having a molecular weight of 100 or more. When at least one of the molecular weights is 1000 or more, the final viscosity of the thickening composition is increased, and the viscosity tends to be increased to a viscosity with good handleability. In this case, the lower limit of the molecular weight is more preferably 50,000 or more, further preferably 10,000 or more, particularly preferably 20,000 or more, and most preferably 30,000 or more. The upper limit of the molecular weight is not particularly limited, but is preferably 1,000,000 or less. When the molecular weight is 1,000,000 or less, the viscosity of the thickening composition composed of the component (A) and the component (B) is reduced, and the viscosity at the initial stage of the mixing is reduced. Material (Y) tends to have good impregnation. The upper limit of the molecular weight is more preferably 800,000 or less, particularly preferably 500,000 or less, and most preferably 300,000 or less. Here, the molecular weight is a weight average molecular weight. Examples of the low molecular weight compound (Am) having a molecular weight of less than 1000 include, but are not particularly limited to, a force S, for example, aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, adipic acid, and sepatic acid; phthalic acid, isophthalic acid Aromatic saturated dicarboxylic acids such as terephthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid and tetrahydroterephthalic acid; aromatic saturated tricarboxylic acids such as trimellitic acid; aromatic saturated tetracarboxylic acids such as pyromellitic acid; fumaric acid And aliphatic unsaturated dicarboxylic acids such as maleic acid, mesacosic acid, citraconic acid and itaconic acid. Further, a polyester-based polymer having a molecular weight of less than 1000 obtained by subjecting a dicarboxylic acid and a diol to a condensation reaction may be used.

As the high molecular weight compound (A p) having a molecular weight of 100 or more, an acid is contained in the polymer molecule. There is no particular limitation as long as the polymer contains two or more functional groups.The polymer may have an acidic group in the side chain of the polymer molecule, or may have an acidic group at the terminal of the polymer molecule. And both may have an acidic group. For example, polymers such as a polyester polymer having an acidic group, a vinyl polymer having an acidic group, and a butyl ester polymer having an acidic group can be used.

In this case, the content of the acidic group in the high molecular weight compound (A p) may be two or more in the polymer molecule, and preferably, the high molecular weight compound (A p) 100 g Medium 0.01 mol or more. When the content is 0.01 mol or more, the reactivity with the component (B) is increased, and the ultimate viscosity is increased, so that the viscosity tends to be increased to a viscosity excellent in handleability. The upper limit of the content is not particularly limited, but is preferably 3 mol or less per 100 g of the high molecular weight compound (A p). When the content is 3 mol or less, the viscosity at the initial stage of mixing of the thickening composition comprising the components (A) and (B) decreases, and the dispersibility of the inorganic filler (F) and the fiber reinforcing material are reduced. (Y) tends to have good impregnation. The lower limit of this content is more preferably at least 0.3 mol, particularly preferably at least 0.1 mol. The upper limit is more preferably 2 mol or less, particularly preferably 1.5 mol or less.

The method for producing the high molecular weight compound (A p) is not particularly limited, and a polymer having two or more acidic groups in one molecule by polymerizing a monomer having one or more acidic groups in one molecule. Coalescence may be obtained, or once a high molecular weight compound (C p) having no acidic group is polymerized, two or more acidic groups are introduced into this high molecular weight compound (C p) to obtain a high molecular weight compound. (A p)

For example, a polyester polymer has an acidic group (carboxyl group) at the end by a method of condensation polymerization of dicarboxylic acid and dihydric alcohol or a method of ring-opening polymerization of acid anhydride and dihydric alcohol. A polyester polymer can be produced. In addition, for example, in the case of a bullet-based polymer, a vinyl monomer having one or more acidic groups in one molecule is homopolymerized or a bullet-based monomer having one or more acidic groups in one molecule is used. A polymer having two or more acidic groups in the side chain can be produced by copolymerizing the monomer and a butyl monomer having neither an acidic group nor a basic group. The butyl monomer having one or more acidic groups in one molecule used in the polymerization is not particularly limited. For example, (meth) acrylic acid, 2- (meth) acryloyloxyshethyl succinic acid, 2- (meth) acryloyloxyshethyl phthalic acid, 2- (meta) acryloyloxyshethylhexahydrophthalic acid, Vinyl monomers containing a strong lipoxyl group, such as fumaric acid, maleic acid, itaconic acid, citraconic acid, monoalkyl fumarate, monoalkyl maleate, monoalkyl itaconate, monoanolealkyl citraconic acid; hydroxy group (E.g., hydroxyxyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate) and acid anhydrides (e.g., phthalic anhydride, methyltetrahydrophthalic anhydride) Acid, nadic anhydride, etc.) Vinyl monomer containing a carboxyl group obtained by the reaction; Bull monomer containing a phosphate group such as mono (2- (meth) acryloyloxyshethyl) acid phosphate; Bull monomer containing a sulfonic acid group Monomers. These may be used alone or in combination of two or more as necessary.

In addition, a vinyl monomer having neither an acidic group nor a basic group, which is used for copolymerization with a vinyl monomer having one or more acidic groups in one molecule, is particularly limited. Not done. For example, methyl (meth) acrylate, alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms, hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 1 to 20 carbon atoms, Acrylic monomers such as benzyl (meth) acrylate, hexyl hexyl (meth) acrylate, isoborenolinole (meta) acrylate, and glycidyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene Examples include monomers, vinyl acetate, and vinyl chloride. Further, among these bullet monomers, it is preferable to use an acrylic polymer obtained by polymerizing an acrylic monomer as a main component as the high molecular weight compound (Αρ).

When a high molecular weight compound (Α ρ) having a molecular weight of 100 or more is used as the component (Α), it is preferable to use it together with a low molecular weight compound having a molecular weight of not more than 100 1. Better. By using a high molecular weight compound (Α ρ) and a low molecular weight compound together, the viscosity of the viscous composition consisting of the (Α) component and the (Β) component decreases at the initial mixing of the viscous composition, and the dispersion of the inorganic filler (F) There is a tendency that the impregnating property and the impregnation property to the fiber reinforcing material (Υ) become good. This low The molecular weight compound is not particularly limited, and may be the above-mentioned low molecular weight compound (Am) having two or more acidic groups in one molecule, or may be the low molecular weight compound having one acidic group in one molecule. Alternatively, a low molecular weight compound (Cm) having neither an acidic group nor a basic group described below may be used. In particular, as the high molecular weight compound (Ap), a high molecular weight compound containing the above-mentioned acrylic polymer as a main component is used, and is dissolved in a low molecular weight compound containing the above-mentioned acrylic monomer as a main component. It is preferably used as an acrylic syrup (SA). '

The content of the component (A) is not particularly limited, but is preferably 0.1 to 99.9% by mass in the total amount of the thickening composition. Within this range, it tends to react with component (B) to increase the viscosity. When the content is within the above range, the reactivity with the component (B) increases, the final viscosity increases, and the viscosity tends to be increased to a viscosity with good handleability. The lower limit of this content is more preferably 1% by mass or more, particularly preferably 5% by mass or more, based on the total amount of the thickening composition. The upper limit is more preferably 90% by mass or less, and particularly preferably 5'0% by mass or less.

The mixing ratio of component (A) and component (B) is not particularly limited, but is preferably in the range of 1Z99 to 99Z1 in terms of the equivalent ratio of acid to base. When the mixing ratio is within this range, the reactivity between the component (A) and the component (B) increases and the ultimate viscosity increases, and the viscosity tends to be increased to a viscosity with good handleability. is there. The mixing equivalent ratio is more preferably 1Z9 to 9/1, and particularly preferably 1Z'3 to 3Z1.

The content of the component (A) is preferably 1 to 50% by mass in the total amount of SMC or BMC. When the content is 1% by mass or more, the reactivity with the component (B) increases, the final ultimate viscosity increases, and there is a tendency that the viscosity can be increased to a viscosity with good handleability. In addition, the viscosity at the initial stage of mixing of the thickening composition comprising the components (A) and (B) decreases, and the dispersibility of the inorganic filler (F) and the impregnation into the fiber reinforcing material (Y) are good. Tend to be. The lower limit of this content is more preferably 3% by mass or more of the total amount of SMC or BMC, and is 5% by mass. /. The above is particularly preferred. The upper limit is more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

Next, the component (B) used in the present invention will be described. The component (B) is a compound having two or more basic groups in one molecule, and the component (B) has two or more basic groups. Due to its inclusion, it reacts with component (A) to increase the viscosity of the entire system. The basic group is not particularly limited, and includes, for example, an amino group, an amide group and the like. Of these, an amino group is preferred from the viewpoint of reactivity with the component (A).

The molecular weight of the component (B) is not particularly limited. It may be a low molecular weight compound (Bm) having a molecular weight of less than 1000 or a high molecular weight compound (Bp) having a molecular weight of 100 or more, but as described above, the component (A) It is preferable that at least one of the components (B) is a compound having a molecular weight of 100 or more.

The low molecular weight compound (Bm) having a molecular weight of less than 1000 is not particularly limited. For example, hexamethylenediamine, triethyleneglyconoresamine, diaminodicyclohexylmethane, bis (aminomethyl) Hexane hexane, N-aminoethylpiperazine, norbornenediamine, m-xylenediamine, mensendiamine, isophoronediamine, bis (2,2,6,6-tetramethyl-4-pyridyl) sebacate, etc. Aliphatic aromatic diamines such as a- (mp-aminophenyl) ethylamine; aliphatic triamines such as diethylenetriamine and N-aminoethylpiperazine; aliphatic tetraamines such as triethylenetetramine; Rangeamine, diaminodiphenylaminomethane, diaminogetyl dimethyldiphenyl Aromatic Jiamin like methane and the like.

The high molecular weight compound (B p) having a molecular weight of 100 or more is not particularly limited as long as it is a polymer containing two or more basic groups in the polymer molecule. The side chain may have a basic group, the polymer molecule may have a basic group at the terminal, or both may have a basic group. For example, a polymer such as a bullet-based polymer having a basic group may be used.

In this case, the content of the basic group in the high molecular weight compound (B p) may be two or more in the polymer molecule, and preferably, the high molecular weight compound (B p) 100 It is 0.01 mol or more in 0 g. When the content is 0.01 mol or more, (A) the reactivity with the component increases, the final ultimate viscosity increases, and the viscosity tends to be increased to a viscosity with good handleability. is there. The upper limit of the content is not particularly limited, but is preferably 3 mol or less per 100 g of the high molecular weight compound (B p). When this content is 3 mol or less, mixing of the thickening composition comprising the components (A) and (B) The initial viscosity decreases, and the dispersibility of the inorganic filler (F) and the impregnation of the fiber reinforcing material (Y) tend to be good. The lower limit of this content is more preferably at least 0.3 mol, particularly preferably at least 0.1 mol. Further, the upper limit is more preferably 2 mol or less, particularly preferably 1.5 mol or less.

The method for producing the high molecular weight compound (B p) is not particularly limited, and two or more basic groups can be formed in one molecule by polymerizing a monomer having one or more basic groups in one molecule. May be obtained, or once a high-molecular-weight compound (CP) having no basic group is polymerized, two or more basic groups are introduced into the high-molecular-weight compound (C p) to obtain a high molecular weight compound. Molecular weight compound (B p).

For example, in the case of a vinyl polymer, a vinyl monomer having one or more basic groups in one molecule is homopolymerized, or a vinyl monomer having one or more basic groups in one molecule is used. -Polymer having two or more basic groups in the side chain by copolymerizing vinyl monomer and vinyl monomer having neither acidic group nor basic group can do.

The vinyl monomer having one or more basic groups in one molecule used in the polymerization is not particularly limited, and examples thereof include N, N-dimethylaminoethyl (meth) acrylate and N, N-gelatin. Vinyl monomers containing an amino group such as tylaminoethyl (meth) acrylate; vinyl monomers containing an amide group such as (meth) atalylic acid amide; and the like. These may be used alone or in combination of two or more as necessary. In addition, a vinyl monomer having neither an acidic group nor a basic group, which is used for copolymerization with a vinyl monomer having one or more basic groups in one molecule, is particularly restricted. It is not limited, and a vinyl monomer having neither the above-mentioned acidic group nor basic group can be used.

Among these butyl-based monomers, it is preferable to use an acryl-based polymer obtained by polymerizing an acryl-based monomer as a main component as the high molecular weight compound (B p).

When a high molecular weight compound (Bp) having a molecular weight of 100 or more is used as the component (B), it is preferably used in combination with a low molecular weight compound having a molecular weight of less than 1000. By using the high molecular weight compound (B p) and the low molecular weight compound together, the viscosity at the initial stage of mixing of the thickening composition comprising the components (A) and (B) decreases, and the inorganic filler The dispersibility of (F) and the impregnation into the fiber reinforcement (Y) tend to be good. The low molecular weight compound used in combination with the high molecular weight compound (Bp) is not particularly limited, and may be the low molecular weight compound (Bm) containing two or more basic groups in one molecule described above, or one molecule. It may be a low molecular weight compound containing one basic group in it, or a low molecular weight compound (Cm) having neither an acidic group nor a basic group described below. In particular, an acrylic syrup obtained by dissolving a high molecular weight compound (Bp) as a high molecular weight compound containing the above-mentioned acrylic polymer as a main component and dissolving it in a low molecular weight compound containing an acrylyl monomer as a main component. (SB) is preferred. .

Although the content of the component (B) is not particularly limited, it is 0.1 in the total amount of the thickening composition.

~ 99.9% by weight is preferred. Within this range, it tends to react with component (A) and become viscous. When the content is within the above range, the reactivity with the component (A) increases, the final viscosity increases, and the viscosity tends to be increased to a viscosity with good handleability. The lower limit of this content is more preferably 1% by mass or more, particularly preferably 5% by mass or more, based on the total amount of the thickening composition. The upper limit is more preferably 90% by mass or less, particularly preferably 50% by mass or less.

The content of the component (B) is 1 to 50 mass in the total amount of SMC or BMC. / ₀ is preferred. When the content is 1% by mass or more, the reactivity with the component (A) increases, and the ultimate viscosity increases, and the viscosity tends to be increased to a good handleability. In addition, the viscosity at the initial stage of mixing of the thickening composition comprising the components (A) and (B) decreases, and the dispersibility of the inorganic filler (F) and the impregnation into the fiber reinforcing material (Y) are good. Tend to be. The lower limit of this content is 3% of the total amount of SMC or BMC. /. More preferably, the content is 5% by mass or more. The upper limit is more preferably 40% by mass or less, and more preferably 30% by mass. / o or less is particularly preferred.

The thickening composition of the present invention comprises a compound (A) containing two or more acidic groups in one molecule and a compound (B) containing two or more basic groups in one molecule as basic constituent components. However, if necessary, it may contain a compound (C) having neither an acidic group nor a basic group.

The molecular weight of component (C) is not particularly limited. Low molecular weight of less than 1000 Compound (C m), or a high molecular weight compound (C p) having a molecular weight of 1000 or more. The low molecular weight compound (Cm) having a molecular weight of less than 1000 is not particularly limited. For example, vinyl-based monofunctional monomers having neither the above-mentioned acidic group nor basic group such as methyl methacrylate, ethylene dalicol di (meth) acrylate, polyethylene glycol di (meth) acrylate 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, neopentinole glycol di (meth) acrylate, Examples include vinyl multifunctional monomers such as trimethylolpropane tri (meth) acrylate, aryl (meth) acrylate, and divinylbenzene. These may be used alone or in combination of two or more as necessary. Of these bi: // monomers, acryl monomers are preferred, and methyl methacrylate is particularly preferred.

The high molecular weight compound (C p) having a molecular weight of 100 or more is not particularly limited. For example, a polymer obtained by polymerizing a butyl monomer having neither the above-mentioned acidic group nor base group can be used. Above all, an ataryl polymer obtained by polymerizing an acrylic monomer as a main component is preferable. '

The content of the component (C) is not particularly limited, but is preferably 1 to 90% by mass based on the total amount of the thickening composition. When the content of the component (C) is 1% by mass or more, the viscosity of the thickening composition at the initial stage of mixing tends to decrease, and the mixing tends to be easy. In addition, when the content of the component (C) is 90 mass% or less, the ultimate viscosity becomes high, and the viscosity tends to be increased to a viscosity with good handleability. The lower limit of this content is more preferably 10% by mass or more, and particularly preferably 20% by mass or more, based on the total amount of the viscous composition. The upper limit is more preferably 0% by mass or less, particularly preferably 50% by mass or less. Further, the content of the component (C) is preferably 1 to 50% by mass in the total amount of SMC or BMC. When the content is 1% by mass or more, the viscosity of the thickening composition at the initial stage of mixing decreases, and the dispersibility of the inorganic filler (F) and the impregnation into the fiber reinforcing material (Υ) tend to be improved. , 50 mass. /. In the following cases, the final attainable viscosity of the thickening composition becomes high, and the viscosity tends to be increased to a viscosity with good handling and properties. The lower limit of this content is 5% of the total amount of SMC or BMC. /. More preferably, 10% by mass The above is particularly preferred. The upper limit is 40 mass. /. The following is more preferred, and the content is particularly preferably 30% by mass or less.

In the present invention, the SMC or BMC can be obtained by blending the inorganic filler (F) with the thickening composition comprising the components (A) and (B) and, if desired, the component (C). it can. The inorganic filler (F) is not particularly limited, and the above-mentioned inorganic fillers can be used.

In the SMC or BMC of the present invention, a resin composition (X) comprising a monomer (m), a polymer (p) and an inorganic filler (F), a fiber reinforcing agent (Y), and a curing agent When the agent (Z) is used as a constituent, it is important that the parameter I (T) represented by the following formula (1) be 0.01 or more at an arbitrary temperature T within the range of 20 to 80 ° C. is there.

I (T) = ta η δ (Τ) -0.0021 Τ-0.0962 (1) where tan S (Τ) is the loss tangent of the resin composition (X) at the temperature Τ and is rheometric. · Measured using the dynamic stress rheometer DSR-200 manufactured by Scientific under the measurement conditions described below. The temperature で is the temperature in degrees Celsius.

Here, the state of the resin thread (X) is not particularly limited. When the components (m), (p) and (F) are mixed and the viscosity does not change after mixing, the state is immediately after mixing, and the components (m), (p) and (F) are mixed. In this case, when a change in viscosity occurs after mixing, the state may be a state immediately after mixing, a state in the course of thickening, or a state after thickening.

Ta η δ (Τ) representing the dynamic viscoelastic behavior of the resin composition (X) is a value (ta η δ) obtained by dividing the loss rigidity G ″ (T) at the temperature Τ by the storage rigidity G ′ (T). (Τ) = G "(Τ) / G '(Τ)), which is an index that indicates the balance between the behavior as a viscous body (loss rigidity) and the behavior as an elastic body (storage rigidity). Therefore, as tan S (T) increases, the behavior as a viscous body becomes dominant at temperature T and tends to flow more easily.Conversely, as tan δ (Τ) decreases, elastic body at temperature Τ increases. Behavior tends to be dominant and difficult to flow. That is, tan S (T) is an index representing the fluidity of the resin composition (X) at the temperature T. This tan S (T) Is dependent on the temperature, so the parameter I (T) is corrected by the temperature T. This parameter I (T) force 0 at any temperature T within the range of 20-80 ° C.

When the ratio is 01 or more, the fluidity in the mold during molding of SMC or BMC becomes good, and a molded article having no underfill and excellent surface smoothness can be obtained. If this parameter I (T) is less than 0.01, the fluidity in the mold during molding of SMC or BMC becomes poor, and the resulting molded product tends to be underfilled. Hereinafter, the fluidity and moldability of the SMC or BMC during molding will be described.

When the fiber reinforcing agent (Y) is contained in the SMC or BMC, the fluidity of the SMC or BMC becomes poor, so that the fiber reinforcing agent (Y) is hardly oriented at the time of molding, and it is difficult to exhibit a capturing effect. Moldability tends to be poor. At the same time, the obtained molded article tends to be underfilled, or the fiber reinforcing agent (Y) tends to emerge on the molded article surface, resulting in poor appearance.

In the case of unsaturated polyester sheet molding compound or balta molding compound, the molecular weight of the unsaturated polyester is several thousand to 10,000, so the resin itself has good fluidity and fiber reinforcement The inclusion of (Y) does not significantly affect the formability.

However, in the case of acryl-based SMC or BMC, the molecular weight of the acryl-based polymer is at least tens of thousands or more. Therefore, when the fiber reinforcing agent (Y) is contained, the flow of the SMC or BMC is higher than when it is not contained. Properties tend to be extremely poor and affect moldability. In particular, in the case of acrylic SMC or BMC, when the content of the fiber reinforcing agent (Y) is as high as 10% by mass or more, this effect tends to be remarkable.

On the other hand, when the SMC or BMC is heated and pressed, the SMC or BMC is heated at room temperature and simultaneously pressurized, and flows while being heated in the mold. Generally, SMC or BMC is in a solid state at room temperature, and its behavior as an elastic body is dominant, so it is difficult to flow, and as the temperature rises, the behavior as a viscous body increases and it tends to flow easily. is there.

In the present invention, the temperature of the resin composition (X) in the mold during the molding is increased. By controlling the viscoelastic behavior (balance between the behavior as a viscous body and the behavior as an elastic body) accompanying this, the formability of SMC or BMC containing the fiber reinforcing agent (Y) is improved. That is, a parameter I (Τ) obtained by correcting tan S (T) of the resin composition (X) by the temperature Τ When the force is 0.01 or more at an arbitrary temperature 内 within the range of 20 to 80 ° C. The SMC or BMC odor X containing the fiber reinforcing agent (Y) also has good fluidity in the mold.

The parameter I (T) may be 0.01 or more at an arbitrary temperature T within the range of 20 to 80 ° C, and the parameter I (T at a temperature below 20 ° C or over 80 ° C. T) is not particularly limited. This is because the viscoelastic behavior within the range of 20 to 80 ° C (that is, within the temperature range at the beginning of flow in the mold) affects the formability.

There is no particular limitation on the lower limit of the parameter I (T) as long as it is at least 0.1, and the force is preferably at least 0.1, more preferably at least 0.2, and particularly preferably at least 0.4. The upper limit of the parameter I (T) is not particularly limited, but is preferably 100 or less, more preferably 20 or less, and particularly preferably 10 or less.

This parameter I (T) is obtained by correcting ta η δ (Τ) of the resin composition (X) at a temperature Τ. As described later, the composition of the polymer in the resin composition (X) Weight average molecular weight, glass transition temperature and amount of added syrup, and, if desired, when divalent metal oxides or hydroxides such as magnesium oxide are used, can be freely controlled by the type and amount of addition. can do.

Next, the resin composition (X) used in the present invention will be described. The resin composition (X) is composed of a monomer (m), a polymer (p), and an inorganic filler (F), and is not particularly limited, but is preferably an ataryl-based resin composition.

The monomer (m) is a component that imparts fluidity to the SMC or BMC of the present invention.

The acrylic monomer used in the component (m) is not particularly limited, but is preferably a monomer having methacryloyl and a Z or acryloyl group, or a mixture thereof.

Specific examples thereof include methyl (meth) acrylate, alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms, and hydroxyalkyl having 1 to 20 carbon atoms. (Meth) acrylates having an ester group having an aromatic ring, such as hydroxyalkyl (meth) acrylates and benzyl (meth) acrylates having a kill group, and cyclohexane rings such as acrylates. ... that having a ester group having the (meth) Atari rate, Isoboru - Le (meth) having an ester group having a bicyclo ring of the Atari rate, etc. (meth) Akurireto, tricyclo [5 2 1 0 ² ^'(; ] Having an ester group having a tricyclo ring such as decanyl (meth) acrylate and (meth) acrylate having an ester group having a fluorine atom such as 2,2,2-trifluoroethyl (meth) acrylate ( It has a cyclic ether structure such as meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl (meth) acrylate, etc. (Meth) acrylate, (meth) acrylic acid, metal salt of (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) ) Acryl monofunctional monomers (ml) such as (meth) atalylate having an amino group such as acrylate and (meth) amide amide; and ethylene glycol di (meth) acrylate and polyethylene glycol ( (Meta) acrylate, propylene dalicol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol; chol (meth) acrylate, 1,4-butylene glycol di (meth) acrylate , Polybutylene recall di (meth) acrylate, neopentyl glycol di (meth) acrylate , 1,6-Hexanediol di (meth) acrylate, 1,9-nonanediol / res (meta) acrylate, 1,10-1 decandiol / resid (meta) acrylate, dimethylo / retethane (meta) Atalate, 1, 1-dimethylone-lup mouth pandi (meth) acrylate, 2,2-dimethylolpropanedi (meth) acrylate, trimethylolethanetri (meta) acrylate, trimethylolpropanetri (meth) T) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, or a polyester of (meth) acrylic acid with a polyhydric alcohol [eg, pentaerythritol, dipentaerythritol, etc.]; Acryl-based polyfunctional monomers such as aryl (meth) acrylate And the like. These can be used alone or in combination of two or more as necessary. In addition to the acrylic monomer, the component (m) includes, for example, aromatic vinyl such as styrene and divinyl benzene, butyl acetate, (meth) acrylonitrile, chloroidene biel, maleic anhydride, maleic acid, and maleate maleate. And monomers such as fumaric acid, fumaric acid ester, and triaryl isocyanurate.

In order to impart mechanical strength, solvent resistance, heat resistance, dimensional stability, and the like to a molded article obtained by using the SMC or BMC of the present invention, a polyfunctional monomer (m) is added to the component (m). m2) is preferably contained. In this case, the content of the polyfunctional monomer (m2) is not particularly limited. However, in order to effectively obtain the above effects, the content of the polyfunctional monomer (m2) should be 3 to 60% by mass in the component (m). preferable. In particular, at least one of neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate as polyfunctional monomers (m2) The use of seeds is preferred because a molded article having a very high surface gloss and excellent hot water resistance can be obtained. In this case, at least one of neopentyl diglycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate and other multifunctional monomers May be used in combination. Among these acrylic monomers (>>!), The use of methyl methacrylate is preferred because the resulting molded article tends to have a marble-like transparency and depth.

In addition, when methyl methacrylate is used as the component (m), when the acryl-based polymer powder described later is used as a thickener and thickened by physical dissolution, the viscosity immediately after the addition of the thickener increases. The impregnating property of the fiber scavenger tends to be poor, but the viscosity after aging of SMC or BMC tends to increase. Conversely, when a polyfunctional monomer (m2) is used as the component (m), when the acrylic polymer powder is used as a thickener and thickened by physical dissolution, The viscosity tends to decrease, and the impregnation into the fiber reinforcing agent tends to be good, but the viscosity after aging of SMC or BMC tends to decrease.

Therefore, when using an acrylic polymer powder as a thickener and thickening by physical dissolution, the thickener can be obtained by using methyl methacrylate and a polyfunctional monomer as the component (m) in combination. Balance between viscosity immediately after addition and viscosity after aging It is preferable to take. Particularly in this case, the viscosity immediately after the addition of the thickener is changed by changing the combination ratio of methyl methacrylate and the polyfunctional monomer according to the composition Z or the molecular weight of the polymer powder used as the thickener. And the viscosity after aging can be controlled.

In the present invention, the content of the component (m) is not particularly limited, but is preferably in the range of 5 to 95% by mass in the resin composition (X) of the present invention. When the content of the component (m) is 5% by mass or more, the fluidity of the SMC or BMC tends to be good, and when the content of the component (m) is 95% by mass or less, curing occurs. The shrinkage rate at the time tends to be low. The lower limit of the content of the component (m) is more preferably 10% by mass or more, and more preferably 15% by mass. /. The above is particularly preferred. The upper limit is more preferably 80% by mass or less, particularly preferably 50% by mass or less.

Next, the polymer (P) used in the present invention will be described. The polymer (P) (1) develops a viscosity suitable for production when producing SMC or BMC, and (2) increases the viscosity to a viscosity that is easy to handle when handling SMC or BMC , And (3) When molding SMC or BMC, it is a component that exerts an action that governs the fluidity during molding.

First, the function (1) of the polymer (P) will be described.

SMC or BMC must be in a solid (clay-like) state without stickiness when handled, but must be low in occupancy to ensure uniform dispersion of each component during manufacture. The viscosity at the time of production differs depending on the equipment, and dispersion tends to be poor if the viscosity is too low or too high. Therefore, the viscosity of the mixture may be adjusted according to the equipment to be used. The viscosity of this mixture depends on the viscosity of the monomer (m), the type of inorganic filler (F) and the amount added. By dissolving at least a part of the component (p) in the component (m) to form a syrup according to the components (m) and (F) to be used, the viscosity at the time of production can be adjusted.

Next, the action of the above (2), that is, the action of the polymer (p) as a thickener will be described.

In order for the polymer (P) to act as a thickener, (i) the polymer (p) is completely dissolved in the monomer (m) in advance to obtain a low-viscosity syrup, (Ii) a method of thickening the system by physically dissolving the powdery polymer (P) in the monomer (m); There are two ways.

In the case of the above (i), the method of increasing the viscosity by reacting the low-viscosity syrup is not particularly limited. However, as described above, a functional group is introduced into the component (p), and the functional group and the SMC are added. Alternatively, the viscosity can be increased by chemically reacting with any component in BMC.

For example, a method of introducing a functional group (for example, a carboxyl group) that reacts with the inorganic filler (F) into the component (p) and causing the inorganic filler (F) to react with the inorganic filler (F) to increase the viscosity. Can be In this case, a divalent metal oxide or hydroxide such as magnesium oxide is added to the system, and the functional group introduced into the component (P), the inorganic filler (F), and the divalent metal oxide are added. The substance or hydroxide may be simultaneously reacted to make it viscous. In addition, for example, a polymer (Ap) in which functional groups A and B (for example, an acidic group and a basic group) that react with each other are separately introduced, and a low-viscosity syrup in which the polymer (Bp) is dissolved are used. There is a method in which the mixture is prepared and reacted by mixing both to increase the viscosity.

In the case of the above (ii), the component (p) acts as a thickener by at least partially dissolving in the component (m), and increases the viscosity of the entire system. Therefore, the component (P) may have the above-mentioned functional group or may not have the functional group.

In the case of (ii), the volume average particle diameter of the powder of the component (p) is preferably in the range of 10 to 500. When the volume average particle diameter is 10 μm or more, the initial thickening rate at the time of coating in the production of SMC can be kept low, and the fiber reinforcing agent (Y) of the resin composition (X) can be reduced. There is a tendency that the impregnating property of the resin becomes good. When the volume average particle size is 500 zm or less, there is a tendency for the component (p) to remain undissolved in the monomer (m), and the resulting molded article tends to have a good appearance. The lower limit of the average particle diameter is more preferably at least 30 μm, particularly preferably at least 70 ^ m. The upper limit is more preferably 350 μm or less, and particularly preferably 200 Atm or less.

In the case of (ii), all of the components (p) may be added as a polymer powder. In order to moderately adjust the viscosity during the production of SMC or BMC, part of component (p) is dissolved in component (HI) in advance and used as syrup, and the rest is used as polymer powder. It may be added.

Although the weight average molecular weight of the component (P) is not particularly limited, the thickening effect tends to increase as the weight average molecular weight increases in both (i) and (ii). preferable. The lower limit of the weight average molecular weight is more preferably 30,000 or more. The upper limit of the weight average molecular weight of the component (P) is not particularly limited in terms of the action as a thickener, but will be described later because it affects the fluidity of SMC or BMC during molding. .

Next, the effect of the above (3), that is, the relationship between the component (p) and the fluidity of the SMC or BMC during molding will be described.

In general, a thickened SMC or BMC consisting of a monomer and a polymer is a mixture of a monomer called a so-called viscous body and a polymer called a so-called elastic body. It is a viscoelastic body having both properties of the body.

As described above, the present invention improves the formability by controlling the balance (ta η δ (Τ)) between the viscous and elastic bodies of SMC or BMC. The viscoelastic behavior of SMC or BMC depends on the temperature of SMC or BMC, the mixture ratio of monomer (m) and polymer (P), composition of polymer (p), weight average molecular weight, glass transition temperature, When the viscosity is increased by a chemical reaction, it depends on the number of reaction points, and by controlling these, the balance between the viscous and elastic bodies (tan S (T)) can be controlled.

For example, as for the temperature of SMC or BMC, the behavior as an elastic body tends to be dominant at lower temperatures, and the behavior as a viscous body tends to be dominant at higher temperatures. As for the mixing ratio of the monomer (m) and the polymer (p), the larger the content of the polymer (p), the more the behavior as an elastic body becomes dominant, and the content of the polymer (p) The smaller the is, the more the behavior as a viscous body tends to be dominant. In the case of SMC or BMC that has become viscous due to a chemical reaction, as the number of chemical reaction points increases, the behavior as an elastic body becomes more dominant, and the number of chemical reaction points decreases. The smaller the amount, the more the behavior as a viscous body tends to be dominant. Also, the composition of the polymer (p) By controlling the viscosity, it is possible to control whether the viscosity is increased by a chemical reaction or the viscosity is increased by physical dissolution. Behavior also differs.

When thickening SMC or BMC by the chemical reaction of component (p), as described above, a functional group may be introduced into component (p), and the smaller the amount of this functional group is, the more viscous the material becomes. The behavior of the elastic body tends to be dominant when the amount of the functional group is large.

When the viscosity is increased by the chemical reaction of the SMC or BMC component ( _P ) (case (i) above), the upper limit of the weight average molecular weight of the component (P) is preferably 500,000 or less. When the molecular weight is 500,000 or less, a viscous behavior tends to appear, and the parameter (I) tends to be able to be set to 0.01 or more. In this case, the upper limit of the weight average molecular weight is more preferably 300,000 or less, and particularly preferably 100,000 or less.

The more preferable range of the weight average molecular weight is the composition (functional group) of the polymer (P), the partner to be reacted (inorganic filler (F), divalent metal oxide or hydroxide, or another functional group B). And the amount of the polymer (B p) etc.) For example, as described above, the number of chemical reaction points also affects the viscoelastic behavior, so when the amount of functional groups introduced into the polymer (P) (the number of chemical reaction points) is large, weight The smaller the average molecular weight, the better. If the amount of functional groups (the number of chemical reaction points) introduced into the polymer (p) is small, the larger the weight average molecular weight, the better. Also, for example, when the activity of the inorganic filler (F), the divalent metal oxide or hydroxide is high, or when the addition amount is large, the weight average molecular weight of the polymer (p) is preferably small, When the activity of the inorganic filler (F), divalent metal oxide or hydroxide is low, or when the amount is small, the polymer (p) preferably has a large weight average molecular weight.

Also, when the SMC or BMC is thickened by the physical dissolution of the component (p) (in the case of (ii) above), there is no chemical reaction point, so the viscosity is higher than in the case of (i). Tend to exhibit a dynamic behavior and flow easily. Therefore, in this case, the upper limit of the weight average molecular weight of the component (P) is preferably 2,000,000 or less. Physical When the weight average molecular weight is less than 200,000, the viscosity tends to be manifested when the viscosity is increased by dissolution.The parameter (I) can be set to 0.01 or more. It tends to be. In this case, the upper limit of the weight average molecular weight is more preferably 150,000 or less, further preferably 500,000 or less, and particularly preferably 100,000 or less. The glass-transition temperature of the component (p) is not particularly limited, but is preferably from 10 to 150 ° C. The more preferable range HI of the glass transition temperature depends on the weight molecular weight of the component (P). When the weight average molecular weight is small, the glass transition temperature is more preferably high. When the weight average molecular weight is large, the glass transition temperature is HI. The temperature is low! /, More preferred! / ,.

As described above, depending on the composition of the component (p) (whether or not it has a functional group that becomes viscous by a chemical reaction) and, if the viscosity is increased by a chemical reaction, the component to be reacted, The preferable range of the weight average molecular weight of p) is different. Further, since the preferred range of the glass transition temperature of the component (P) varies depending on the weight average molecular weight of the component (P), the composition, addition amount, weight average molecular weight, glass transition temperature, chemical When the viscosity is increased by an appropriate reaction, the aforementioned parameter I (T) can be controlled by appropriately combining the reaction partner and. The method for producing the component (p) is not particularly limited, and polymerization can be performed by a method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or a bulk polymerization method. Methods for obtaining polymer powder from the polymer obtained by each polymerization method include, for example, filtration and drying of the suspension in the case of suspension polymerization, and spraying of the emulsion in the case of emulsion polymerization. Polymer powder by drying, freeze-drying or coagulation → drying, by pulverization in the case of bulk polymerization, or by degassing → pulverization or reprecipitation → filtration → drying in the case of solution polymerization Can be obtained.

When the component (p) is reacted with an inorganic filler (F) or a divalent metal oxide or hydroxide to make it viscous, the aforementioned acid monomer (for example, (meth) acrylic acid or the like) is used. ) May be copolymerized. When the components (p) are allowed to react with each other to increase the viscosity, one obtained by copolymerizing the above-mentioned acid monomer (for example, (meth) acrylic acid or the like) as one component (A p) is used. And the other component (B p) copolymerized with the aforementioned basic monomer (eg, N, N-dimethylaminoethyl (meth) acrylate). May be used.

In the present invention, the content of the component (p) is not particularly limited, but is 1 to 35 mass in the resin composition (X). It is preferably within the range of / ₀ . When the content is 1% by mass or more, a high viscosity effect tends to be obtained, and when the content is 35% by mass or less, the fluidity of SMC or BMC during molding tends to be good. . The lower limit of the content of the component (p) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Further, the upper limit ^ t is more preferably 30% by mass or less, and particularly preferably 25% by mass or less. As described above, the preferable range of the content of the component (p) varies depending on the composition, the weight average molecular weight, and the glass transition temperature of the component (p).

The component (p) is not particularly limited, but is preferably an acrylic polymer from the viewpoint of weather resistance.

The resin composition (X) used in the present invention comprises the above components (m), (p) and (F) as basic constituents, and further comprises a stone pattern material (W). By molding, a granite-like resin molded product having a stone pattern can be obtained. The stone pattern material (W) is not particularly limited, and examples thereof include resin particles and resin particles containing an inorganic filler. The resin (W1) constituting the stone pattern material (W) is not particularly limited.

Specific examples of the resin (W1) include an acrylic resin, a vinyl ester resin, an unsaturated polyester resin, an epoxy resin, a saturated polyester resin, a polycarbonate resin, a polyolefin resin, a phenol resin, and a polyvinyl chloride resin. . Among them, acrylic resin is preferable.

When the stone pattern and (W) are resin particles containing an inorganic filler, the inorganic filler (W2) is not particularly limited. Specific examples thereof include, for example, aluminum hydroxide, silica, fused silica, calcium carbonate, barium sulfate, titanium oxide, and glass powder. Among them, aluminum hydroxide, silica, fused silica, and calcium carbonate And at least one selected from glass powder.

When the stone pattern material (W) is used in the present invention, one type of the stone pattern material may be used, or two or more types having different colors and particle sizes may be used in combination. Further, the stone pattern material (W) may contain a pigment (W3) as necessary. The content of the stone pattern material (w) is not particularly limited, but in the resin composition (X), it is 0.1; It is preferably in the range of / ₀ . (W) The content of the component is 0.1 mass. When the ratio is / ₀ or more, a stone pattern with good design properties tends to be obtained, and the mass is 40 mass. When the ratio is / ₀ or less, the fluidity during molding of SMC or BMC tends to be good. The lower limit of the content of the component (W) is more preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of the component (W) is 30 mass%. / _{0 or} less, more preferably 20 mass. / ₀ or less is particularly preferred.

The method for producing the stone pattern material (W) is not particularly limited, and examples thereof include a method of pulverizing a resin plate or a resin molded product containing an inorganic filler. The method of pulverization in this case is not particularly limited, for example, pulverization using a crusher or the like. The stone pattern material (W) obtained by pulverization may be used as it is, or may be used after being appropriately classified for each particle size using a sieve or the like.

In the resin composition (X) used in the present invention, in addition to the above stone pattern material (W), if necessary, a thickener such as the above-mentioned divalent metal oxide or hydroxide, Various additives such as a coloring agent, a low shrinkage agent, an internal mold release agent, and a viscosity reducing agent can be added.

In the SMC or BMC of the present invention, the content of the resin composition (X) is not particularly limited, but is preferably in the range of 20 to 99% by mass based on the total amount of the SMC or BMC. When the content of the resin composition (X) is 20% by mass or more, the fluidity of SMC or BMC at the time of molding tends to be good. Target strength tends to increase. The lower limit of the content of the resin composition (X) is more preferably 50% by mass or more, and is 60% by mass. / ₀ or more is particularly preferred. The upper limit of the content is more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

The complex viscosity of the resin composition (X) is 30. Is preferably in the range of ^{l X l 0 3 P a '} s ~l X l 0 7 P a' s in C. When the complex viscosity at 30 ° C is 1 × 10 ³ Pa · s or more, the stickiness of SMC or BMC disappears, and the handleability tends to be good. Further, when molding the SMC or BMC, bubbles contained in the SMC or BMC tend to be easily removed, and the appearance of the obtained molded article is improved. When the complex viscosity at 30 ° C is 1 X 10 ⁷ Pas or less, SM C or BMC tends to be cut, and handling is improved.

Here, the complex viscosity at 30 ° C. of the resin composition (X) is the complex viscosity at 30 ° C. of the resin composition (X) aged and thickened. This is a dynamic viscosity measured with a dynamic stress rheometer DSR-200 manufactured by Tific Corporation under the measurement conditions described below.

30 of the resin composition (X). Complex viscosity at C, if the range of ^{l X 10 3 P a · s~l} X 1 0 7 P a · s, but are not limited, the lower limit is 2 X 10 ³ P a · s or more, more preferably 3 × 10 ³ Pa · s or more, and most preferably 1 × 10 ⁴ Pa · s or more. The upper limit is more preferably less ^{_{8 X 10 6 P a · S}} , 5 X 10 6 P a - s or less is particularly ^{preferred, l X 10 6 P a '} s less is most preferred. The complex viscosity at 80 ° C of the resin composition (X) is preferably not more than 0.2 times the complex viscosity at 30 ° C.

SMC or BMC is heated and pressurized at the time of heat and pressure molding, so it flows while being heated in the mold. Therefore, it is possible to improve the moldability of the SMC or BMC containing the fiber reinforcing agent (Y) by controlling the resin viscosity behavior accompanying the temperature rise of the resin composition (X) in the mold during molding. It becomes possible. In general, when a fiber reinforcing agent (Y) is added to SMC or BMC, the viscosity of the SMC or BMC increases and, at the same time, the fiber reinforcing agent (Y) itself contains air bubbles. Tend to be contained. These bubbles tend to escape during flow if the viscosity of the SMC or BMC is high. However, if the viscosity of SMC or BMC is high, the fluidity becomes low, the molded product becomes underfilled, or the fiber reinforcing agent (Y) appears on the surface of the molded product, resulting in poor appearance. The reinforcing agent (Y) is less likely to be oriented, and tends to have less reinforcing effect.

On the other hand, when the viscosity of the SMC or BMC is low, the fluidity of the SMC or BMC in the mold increases, so that even if the fiber reinforcing agent (Y) is contained, the SMC or BMC can reach every corner of the mold. At the same time as filling, the fiber reinforcing agent (Y) tends to be oriented at the time of molding, and the reinforcing effect tends to be easily exhibited. However, if the viscosity of SMC or BMC is low, air bubbles contained in SMC or BMC may cause The flow tends to be difficult to remove during the flow, and defects due to air bubbles tend to occur in the molded product.

Therefore, the viscosity of the SMC or BMC of the present invention is high in the early stage of flow in the mold (that is, when the temperature of the SMC or BMC is low), and in the middle to late stages of flow (that is, when the temperature of the SMC or BMC rises). ) Is preferably lower. After examining the conditions for resolving these two conflicting defects, the present inventors found that the complex viscosity of the resin composition (X) obtained by aging the resin composition (X) was (i) 30 ° C In the range III of 1 X 10 ³ Pa · s to 1 × 10 ⁷ Pa · s, and (ii) the complex viscosity at 80 ° C is 0 · 2 of the complex viscosity at 30 ° C. It has been found that by using a resin composition that is less than or equal to 2 times (generally 0.00001 to 0.2 times), SMC or BMC satisfying the above two conflicting performances can be obtained.

The upper limit of the complex viscosity at 80 ° C of the resin composition (X) is not particularly limited as long as it is 0.2 times or less the complex viscosity at 30 ° C. More preferably, it is particularly preferably 0.15 times or less. The lower limit is preferably at least 0.0000 times the complex viscosity at 30 ° C, more preferably at least 0.0001 times, particularly preferably at least 0.001 times.

The viscosity of the resin composition (X) immediately after mixing and the control of the complex viscosities (i) and (ii) are controlled by the composition of the polymer in the resin composition (X), the weight average molecular weight, and the glass as described later. Freely depending on the transition temperature and the amount of addition, the type of monofunctional monomer and polyfunctional monomer in the resin composition (X), the combination ratio, the amount added, and the type and amount of thickener Can be controlled.

As a specific example, a case of thickening due to physical dissolution when a polymer powder is used as a thickener will be described below.

In this case, when methyl methacrylate is used as the component (m), the viscosity immediately after the addition of the thickener increases when the polymer powder is used as the thickener, and the impregnating property tends to deteriorate. However, the viscosity after aging of SMC or BMC tends to increase. Conversely, when the polyfunctional monomer (m2) is used as the component (m), the viscosity immediately after the addition of the thickener is reduced when the polymer powder is used as the thickener, and the impregnation property is improved. However, the viscosity after aging of SMC or BMC tends to decrease. Therefore, in the present invention, it is preferable to use methyl methacrylate and a polyfunctional monomer as component (m) in combination to balance the viscosity immediately after adding the viscosity agent and the viscosity after aging. In particular, 粘度 By changing the combination ratio of polyfunctional monomers such as methyl methacrylate according to the composition and Z or molecular weight of the polymer powder used as a thickener, the viscosity immediately after adding the thickener and the aging The viscosity can be controlled later.

In this case, the weight average molecular weight of the polymer powder used as a thickener is not particularly limited, but is preferably 200,000 or less. This is because by setting the weight average molecular weight to 200,000 or less, the complex viscosity of the resin composition (X) at 80 ° C. becomes 0.0 O 0 O 1 to 0.2 times the complex viscosity at 30 ° C. It tends to be able to be controlled. The upper limit of the polymer powder weight average molecular weight is more preferably 180,000 or less, and particularly preferably 150,000 or less. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 10,000 or more, more preferably 30,000 or more, and particularly preferably 50,000 or more.

The glass transition temperature (hereinafter, abbreviated as Tg) of the polymer powder used as the thickener is not particularly limited, but is preferably in the range of 50 to 150 ° C. When the Tg of the polymer powder is 50 ° C. or more, the complex viscosity at 30 ° C. of the resin composition (X) tends to be 1 × 10 ³ Pa · s or more, and is 150. When the temperature is below C, the complex viscosity at 80 ° C tends to be 0.0001 to 0.2 times the complex viscosity at 30 ° C. The lower limit is more preferably at least 60 ° C, particularly preferably at least 70 ° C. Further, the upper limit of the T g is more preferably 140 ° C. or lower, and particularly preferably 130 ° C. or lower.

平均 The average particle size of the polymer powder used as the viscosity agent is not particularly limited, but is preferably in the range of 30 to 450 µκι. Here, the average particle diameter means a primary average particle diameter. When the average particle size of the polymer powder is 30 μm or more, it is possible to suppress the initial viscosity at the time of coating when manufacturing SMC, and to manufacture SMC containing a fiber reinforcing agent (Y). In this case, the resin composition (X) tends to have good impregnation with the fiber scavenger (Y). When the average particle size is 450 / zm or less, molding defects (pinholes) due to the undissolved thickener tend to be less likely to occur. The lower limit of the average particle size of the polymer powder is more preferably 50 am or more, and particularly preferably 80 μΐη or more. Also, this The upper limit of the average particle diameter is more preferably 400 // m or less, particularly preferably 300 μm or less.

In the present invention, the content of the polymer powder used as the thickener is not particularly limited, but is preferably in the range of 1 to 35% by mass in the resin composition (X). When the content of the polymer powder is 1% by mass or more, a sufficient thickening effect tends to be exhibited, and the amount is 35% by mass. /. In the following cases, the complex viscosity at 80 ° C of the resin composition (X) can be controlled so as to be 0.001 to 0.2 times the complex viscosity at 30 ° C. There is a tendency. The lower limit of the content of the polymer powder is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less, and 25% by mass. / ₀ or less is particularly preferred. In particular, when resin particles containing an inorganic filler are used as the stone pattern material (W), the complex viscosity at 80 ° C. of the resin composition (X), which is a constituent requirement (ii) of the present invention, However, the complex viscosity at 30 ° C. is preferably in the range of 0.001 to 0.2 times the complex viscosity.

The fiber reinforcing agent (Y) used in the present invention is a component that imparts mechanical strength to the obtained resin molded product, and is not particularly limited. Specific examples of the component (Y) include glass fiber, carbon fiber, polyester fiber, nylon fiber, acrylic fiber, polyethylene fiber, polypropylene fiber, polybutyl alcohol fiber, aramide fiber, and phenol fiber. These can be used alone or in combination of two or more as necessary. In particular, glass fibers and carbon fibers are preferred because they tend to easily exhibit strength.

The length of the component (Y) is not particularly limited, but is preferably in the range of 1 to 6 O mm. The lower limit of the length of the component (Y) is more preferably 5 mm or more, and the upper limit is more preferably 50 mm or less.

In the SMC or BMC of the present invention, the content of the component (Y) is not particularly limited, but is preferably in the range of 1 to 50% by mass based on the total amount of the SMC or BMC. When the content of the component (Y) is 1% by mass or more, the strength of the obtained resin molded article tends to increase, and the weight is 50%. /. In the following cases, the fluidity during molding tends to be good. The lower limit of the content of component (Y) is 5 mass. /. More preferably, the content was 10% by mass or more, more preferably 15% by mass. /. The above is particularly preferred. The upper limit is 40% by mass or less. It is more preferably, and particularly preferably 35% by mass or less.

The ultraviolet absorber (U) and the light stabilizer (L) used in the present invention are components for imparting weather resistance to the resin molded product.

By using the ultraviolet absorber (U), discoloration (yellowing) of the resin component due to poor weather resistance is suppressed, and the resin molded article of the present invention becomes a molded article having excellent weather resistance. The term “resin component” used here refers to the part of the molded product excluding the fiber reinforcement (Y).

The ultraviolet absorber (U) is not particularly limited, but is preferably a compound having a maximum absorption wavelength in a wavelength range of 280 to 380 nm. Among them, at least one compound selected from the group consisting of a benzophenone-based compound, a benzotriazole-based compound, a triazine-based compound, a cyanoacrylate-based compound, and a salicylate-based compound is preferable.

Among them, a benzotriazole compound represented by the following general formula (I) is most preferable.

(In the formula, 1 ^ and R ₂ represent a hydrogen atom or an alkyl group.)

1 ^ in the benzotriazole compound represented by the general formula (I) is not particularly limited as long as it is a hydrogen atom or an alkyl group, but is preferably an alkyl group.

Is an alkyl group, the alkyl group may be substituted with a benzene ring or another substituent. Is an alkyl group, the discoloration (yellowing) of the resin part of the resin molded product tends to be excellently suppressed. R ₂ is not particularly limited as long as it is a hydrogen atom or an alkyl group. When R ₂ is an alkyl group, the alkyl group may be substituted with a benzene ring or another substituent.

Specific examples of the compound represented by the general formula (I) include Tinuvin P, Tinuvin PS, Tinuvin 900, and Tinuvin 32 manufactured by Ciba Shariti Chemicals Co., Ltd. 0, Tinuvin 328, Tinuvin 171, Tinuvin 1 130, Tinuvin 384, li Adecastab LA-31 manufactured by Denka Kogyo Co., Ltd., RUVA93 manufactured by Otsuka Chemical Co., Ltd. (all are trade names). Among these, Tinuvin 900, Tinuvin 320, Tinuvin 328, Tinuvin 171, Tinuvin 1 130, Tinuvin 384, LA-31, and RUVA 93, where 1 ^ is an alkyl group or a substituted alkyl group, preferable. These can be used alone or in combination of two or more as necessary.

The content of the component (U) is not particularly limited, but is preferably in the range of 0.001 to 1% by mass based on the total amount of the SMC or BMC of the present invention. When the content of the component (U) is within this range, discoloration (yellowing) of the resin portion of the resin molded article tends to be suppressed. The lower limit of the content of the component (U) is more preferably 0.01% by mass or more, particularly preferably 0.03% by mass or more, and the upper limit is 0.8% by mass. / ₀ or less, more preferably 0.5% by mass or less.

In the present invention, by using the light stabilizer (L), it can be imparted to a molded article having excellent weather resistance. That is, the obtained resin molded product deteriorates with time, specifically, the deterioration of the interface between the resin portion and the fiber reinforcing agent (Y) with time, and the whitening of the resin molded product due to the discoloration with time (hereinafter referred to as “interface”). Over time). In particular, by suppressing deterioration over time, the emergence of the fiber reinforcing agent (Y) is suppressed, and as a result, it is possible to increase the gloss retention of the molded article. The light stabilizer (L) is not particularly limited, but is preferably a hindered amine compound. Specific examples of the hindered amine-based compound include Tinuvin 123 manufactured by Ciba Chemical Corporation, Adeshi Stub LA_63P manufactured by Asahi Denka Kogyo Co., Ltd. LS-770, SANOL LS-765, SANOL LS-2626, etc. (all are trade names). Of these, Tinuvin 123, Sanol LS-770, Sanol 3-765, and ADK STAB LA-63P are preferred. These can be used alone or in combination of two or more, if necessary.

Although the content of the component (L) is not particularly limited, it is 0.001 to 1 mass in the total amount of the (meth) SMC or BMC of the present invention. The range of / ₀ is preferred. The content of component (L) is within this range. When it is within the range, the deterioration with time of the interface between the resin of the resin molded product and the fiber reinforcing agent (Y) tends to be suppressed. The lower limit of the content of the component (L) is more preferably 0.01% by mass or more, and particularly preferably 0.03% by mass or more. The upper limit is more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less.

In the present invention, by using an ultraviolet absorber (U) and a light stabilizer (L) in combination, discoloration of the resin molded article after the weather resistance test (yellowing of the resin component, and resin component and fiber reinforcing agent) Of the fiber reinforcement over time) and the parameter J described later can be set to 0.1 or more. A resin molded article having an excellent high gloss retention can be obtained.

To the SMC or BMC of the present invention, various additives such as a polymerization inhibitor, a colorant, a low-shrinkage agent, and an internal mold release agent may be added, if necessary, in addition to the above components.

Further, the SMC or BMC of the present invention is not particularly limited, but is preferably an acryl-based SMC or BMC from the viewpoint of weathering resistance.

Next, the method for producing SMC or BMC of the present invention will be described.

The SMC of the present invention is obtained by, for example, mixing the above-mentioned monomer (m), polymer (p), inorganic filler (F), and, if desired, a mixture of various additives on two release films. After applying the mixture, the fiber-reinforcing agent (Y) is added to the surface of one of the release films to which the mixture is applied, and the surface on which the mixture of the other film is applied is superimposed on that surface, and the fiber-reinforcing agent (Y ) Is impregnated with the above mixture and then thickened.

Further, in order to obtain a granite-like SMC having a stone pattern, a mixture containing a stone pattern material may be used in the above-mentioned manufacturing process, and production may be performed in the same manner.

In the production of SMC, the viscosity of the mixture at the time of application to the release film is not particularly limited, but is preferably in the range of 1 to 200 Pa · s. Here, the viscosity of the mixture at the time of coating is a viscosity measured by a BH type viscometer. When the viscosity of the mixture at the time of coating is 1 Pa · s or more, the mixture does not leak from the release film in the step of impregnating the fiber with the strong agent (Y). In addition, when the viscosity of the mixture at the time of coating is 2◦0 Pa · s or less, There is a tendency that the impregnation with the agent (Y) is improved. The lower limit of the viscosity of the mixture during coating is more preferably 2 Pa · s or more. The upper limit is more preferably 100 Pa · s or less.

The aging condition for thickening the mixture is not particularly limited as long as it is 25 ° C or more, but when aging at 25 to 60 ° C for 1 day or more, the viscosity proceeds to the finally reached viscosity. It is preferable because the viscosity tends to end completely. The lower limit of the temperature during aging is more preferably 40 ° C or higher, and the upper limit is more preferably 50 ° C or lower! / ,.

The BMC of the present invention can be produced, for example, by mixing a monomer (m), a polymer (p), an inorganic filler (F), a fiber reinforcing agent (Y), and, if desired, various additives. it can. The mixing method at this time is not particularly limited as long as it is a method capable of efficiently mixing a high-viscosity substance. Specifically, for example, a kneader, a mixer, a roll, an extruder, a kneading extruder and the like can be used.

In the case of BMC, a thickener with a fast thickening rate may be used to increase the viscosity during kneading, or a thickener with a slow thickening rate may be used, and after kneading, ripening after aging. May be. The condition for aging is not particularly limited as long as it is 25 ° C. or higher, but aging at 25 to 60 ° C. for 1 day or more is preferable. When aged under these conditions, the thickening is completely terminated, and the thickening tends to progress to the viscosity finally reached. The lower limit of the aging temperature is more preferably 40 ° C or higher, and the upper limit is more preferably 50 ° C or lower! / ,.

Next, the resin molded product of the present invention will be described.

The resin molded product of the present invention contains the inorganic filler (F) and the fiber reinforcing agent (Y) described above, and has a black panel temperature of 63 ° C and a rainfall of 12 minutes out of 60 minutes using a sunshine analyzer. After the accelerated exposure test for 1,500 hours under the above conditions, the gloss retention of the molded article after the test is 70% or more, and the parameter J represented by the following formula (2) is 0.1 or more.

J = 26-0.276 L * -AE * _ab (2) ■

Here, L * is the lightness index specified in JISZ 8729, which is the value of the lightness index before the accelerated exposure test of the resin molded product. AE * _ab is the color difference specified in JISZ8730, that is, the color difference between the resin molded product before the accelerated exposure test and after the accelerated exposure test. The values of AE * _ab before and after the accelerated exposure test were obtained using the sunshine super mouth life meter WEL-SUN-IIC-B type manufactured by Suga Test Instruments Co., Ltd. Accelerated exposure test was conducted for 1.5 hours under conditions of rainfall of 12 minutes out of 60 minutes at 3 ° C.

The color difference AE * _ab after the accelerated exposure test differs depending on the color intensity (brightness) of the resin molded product before the test, even when the test is carried out under the same conditions, and the resin molding of the dark color (the lightness index L * is small) The color difference ΔE * _ab tends to be larger for a product. Therefore, by introducing the parameter J in which the color difference ΔE * _ab is corrected by the brightness index L * of the resin molded product before the test, it becomes possible to determine the weather resistance regardless of the color of the resin molded product.

The resin molded product of the present invention can be subjected to a long-term accelerated exposure test of 150 hours to determine the weather resistance of the molded product.

This parameter J has a correlation with the weather resistance of the obtained molded article, and the higher the value of the parameter J, the better the weather resistance. The present inventors have found that if the parameter J force is S 0.1 or more, it is a molded article having excellent weather resistance of a degree suitable for outdoor use. When this parameter J is less than 0.1, the weather resistance tends to be poor. Particularly when the parameter J is a negative value, discoloration is severe when used outdoors, and it is used outdoors. Tends to be difficult. This parameter J is preferably 0.5 or more, more preferably 1 or more, particularly preferably 3 or more, and most preferably 5 or more.

In the molded article of the present invention, the gloss retention after the accelerated exposure test was 70. /. That is all. Further, the gloss retention after the accelerated exposure test is preferably at least 75%, more preferably at least 80%, particularly preferably at least 85%, most preferably at least 90%. The resin molded product of the present invention is not particularly limited, but is preferably an acrylic resin molded product from the viewpoint of weather resistance.

The method for producing the resin molded product of the present invention is not particularly limited. For example, it can be produced by subjecting SMC or BMC obtained by the above method to heat and pressure curing. A known method can be used as the method of curing by heating and pressing, and for example, a compression molding method can be used.

The heating temperature is not particularly limited, but is preferably within a range of 80 to 150 ° C. Heating temperature When the temperature is 80 ° C or higher, the curing time of SMC or BMC can be shortened, productivity tends to be high, and the fluidity of SMC or BMC in the mold can be improved. There is a tendency. When the heating temperature is 150 ° C. or lower, the linear shrinkage of the obtained molded article tends to be low, and the gloss of the obtained molded article tends to be good. The lower limit of the heating temperature is more preferably at least 90 ° C, particularly preferably at least 105 ° C. The upper limit of the heating temperature is more preferably 140 ° C or lower, particularly preferably 135 ° C or lower. In the case of performing heat-press molding, the upper mold and the lower mold may be heated with a temperature difference.

The pressurizing pressure is not particularly limited, but is preferably 0.5 to 25 MPa. When the pressure is 0.5MPa or more, the filling of the SMC or BMC into the mold tends to be good, and when it is 25MPa or less, a good molded appearance without whitening can be obtained. There is a tendency. The lower limit of the pressure is more preferably IMPa or more, and the upper limit is more preferably 2 OMPa or less.

The curing time among the heating and pressure curing conditions is not particularly limited, and may be appropriately selected depending on the desired thickness of the resin molded product.

Hereinafter, the present invention will be described specifically with reference to examples. The parts in the examples are on a mass basis.

Physical Properties of Polymer Powder>

[Weight average molecular weight]

It was determined by the polystyrene equivalent value by the GPC method, and was measured under the following conditions according to the range of the weight average molecular weight.

(When the weight average molecular weight is 100,000 or less)

Equipment: High-speed GPC equipment HLC—81 20 manufactured by Tosoh Corporation

Column: Tosoh Corporation, TSKg e 1 G 2000 «[1 ^ and 31 31 ^ § e 1 G 4000 HXL are connected in series.

Open temperature: 40 ° C

Eluent: tetrahydrofuran

Sample concentration: 0.4% by weight

Flow rate: 1 ml / min Injection volume: 0.1 ml

Detector: R I (differential refractometer)

(When the weight average molecular weight is more than 100,000 and less than 1 million)

Equipment: Tosoh Corporation, high-speed GPC equipment HLC-8020

Column: 3 TSKg e 1 GMHXL manufactured by Tosoh Corporation connected in series Oven temperature: 38 ° C

Eluent: Tetrahydrofuran

Sample concentration: 0.4% by weight

Flow rate: 1 ml / min

Injection volume: 0.1 ml

Detector: R I (differential refractometer)

[Volume average particle size]

Laser diffraction Measured using a Z-scattering particle size distribution analyzer (LA-910, manufactured by HORIBA, Ltd.).

[Glass transition temperature (Tg)]

When the polymer is a copolymer polymerized from n kinds of monomers, the following formula (3) is obtained from the glass transition temperature (° C) of the homopolymer of the constituent η kinds of monomer components. ) And rounded off to the nearest whole number. For the glass transition temperature of the homopolymer, the value of “Polymer Data Handbook” edited by the Society of Polymer Science, Japan was used.

Tg: glass transition temperature of the copolymer (° c)

T g ₍₁₎ : Glass transition temperature of the i-component homopolymer (° c)

: Mass ratio of i component, ∑ Wi = l

[Initial viscosity (viscosity immediately after thickener addition)]

In a thermostatic water bath maintained at 30 ° C., measurement was performed with a BH type viscometer manufactured by Tokimec Co., Ltd. using a No. 5 port at a rotation speed of 2 to 20 rpm.

[Dynamic viscoelasticity] The sample was placed on the jig at the lower part of the measuring section, a humidity cover with a pad impregnated with methyl methacrylate was attached, and the upper jig was lowered to make the gap interval 2 mm. After removing the sample protruding from the upper jig, the reservoir of the humidity cover was filled with methyl methacrylate, and aged at 20 ° C so that the measurement part was filled with saturated vapor of methyl methacrylate. After aging for 30 minutes, heating was started and the dynamic viscoelasticity was measured to determine the complex viscosity and ta η δ (Τ). Next, using the obtained ta η δ (T), a parameter I (Τ) was obtained from the following equation.

I (Τ) = t a η δ (Τ) -0.0021 Τ- 0.0962… (1)

(In the formula, t an S (T) is a loss tangent at the temperature T of the resin composition (X), and the temperature Τ is a degree Celsius.)

The measurement conditions of the dynamic viscoelasticity are as follows.

Equipment: Dynamic Stress Rheometer DS R-200 (Rheometrics Scientific Ick)

Measuring part upper jig: Parallel plate with solvent trap (diameter 25 mm) Measuring part lower jig: Peltier type jig

Measuring unit cover: Hyu medium cover

Measuring mode: Dynamic tempering 'Lamp' default Test Temperature control: Peltier method

Temperature conditions: initial temperature = 20 ° C, final temperature = 120 ° C, heating rate = 100 ° C / min

Measurement interval: Every 1 second Gap interval between upper jig and lower jig: 2mm

Frequency: 10 r a d / s

Properties of SMC or BMC>

[Releasability]

The release film was peeled off from the obtained SMC. The state of the film peeling was evaluated as described below.

O: No stickiness on SMC surface, good peeling

X: The release state is not good, such as the SMC adheres to the release film or cannot be released. Good

[Sticky]

The surface condition of SMC obtained in the film peeling test was evaluated as follows. :: The surface from which the film was peeled was not sticky, and the handleability was good.

〇: There is slight stickiness on the surface from which the film has been peeled, but there is no practical problem.

X: The surface from which the film was peeled was sticky, and handling was difficult.

[Impregnation]

The impregnation of the resin composition with the fiber reinforcing agent in SMC or BMC was visually evaluated as follows.

A: The glass fiber is sufficiently impregnated with the resin composition.

〇: The glass fiber is not slightly impregnated with resin, but there is no practical problem.

X: A portion where the resin is not impregnated in the glass fiber is observed.

XX: The glass fiber is hardly impregnated with the resin composition. When the film is peeled, peeling is observed in the glass fiber layer.

[Appearance 3

The surface condition (the presence or absence of air bubbles, the convexity of the glass fiber) of the obtained molded article was visually evaluated as follows.

· Bubbles

◎: The molded article has no air bubbles and the appearance is extremely good.

〇: The molded product has some air bubbles, but at a level that is not problematic for practical use, and the appearance is good.

X: Molded product has air bubbles and appearance is poor.

XX: The molded product has many bubbles and the appearance is extremely poor.

• Glass fiber convex

：: There is no unevenness of the glass fiber, and the appearance is extremely good.

〇 +: The glass fiber has almost no irregularities, and the appearance of tato is good.

〇: Although there are some irregularities in the glass fiber, this is a level that is not problematic in practical use. X: The glass fiber has large convexity and poor appearance.

[Heat-resistant water 'I raw]

The molded plate was immersed in hot water at 98 ° C for 120 hours, and the appearance of the plate before immersion was visually compared.

A: No convex or blistering is observed on the molded product, and the discoloration is small.

〇 +: No protrusion or blistering is observed on the molded product, and the color slightly changes, but there is no practical problem. 〇: The discoloration is small, and the molded product is slightly convex and blistering occurs, but does not cause any problem in practical use.

X: Notably convex and blistering occur on the molded product, which is a practical problem.

[Missing meat]

The underfilled state of the obtained molded article was visually evaluated as follows.

〇: There is no underfill in the molded product.

X: The molded product has underfill.

[Weather resistance (accelerated exposure test)]

Molded with Suga Test Machine Co., Ltd.'s Sunshine Super Long Life Analyzer WEL-SUN-HC-B, with black panel temperature of 63 ° C, 12 minutes out of 60 minutes with rain (spray) The product was subjected to an accelerated exposure test for 1,500 hours, and the gloss retention, the color difference ΔΕ * _β¾ , and the _{protrusion of} the glass fiber after the test were evaluated under the following conditions.

• Gloss retention rate

Based on JIS K7105, the 60-degree specular gloss of the molded product was measured with a handheld gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd. Based on the gloss before the accelerated exposure test and the gloss after the accelerated exposure test, Of the sample before the test was determined.

'Color difference AE * _ab

Based on JISZ 8729, the lightness index L * and the chromaticness index a *, b * of the molded product were measured with a spectroscopic colorimeter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. before and after the accelerated exposure test. From the values of L *, a *, b *, after the exposure test, the color difference AE * _ai specified in _JISZ8730 was determined.

• Embossing of glass fiber

The molded article after the accelerated exposure test was visually evaluated. 〇: No protruding glass fiber

X: Glass fiber ¾1 protruding

-Overall evaluation of weather resistance

The gloss retention, color difference AE * _ab , and embossing of the glass fiber were comprehensively evaluated.

◎ +: extremely good

◎: very good

〇: good

X: Bad

(1) Example of polymer production

[Production Example 1] Production example of ataryl polymer (p-1)

In a reactor equipped with a cooling pipe, thermometer, stirrer, and nitrogen inlet pipe, 435 parts of pure water and 1 part of polyvinyl alcohol (88% saponification, 1000 degree of polymerization) were dissolved, and then methyl methacrylate was dissolved. 291 parts, 9 parts of methacrylic acid, 0.39 parts of octyl thioglycolate, and 0.6 parts of azobisisobutyl mouth-tolyl are added, and the mixture is stirred at 350 rpm under a nitrogen atmosphere. The temperature was raised to 70 ° C. in 1 hour, and heating was continued for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours, and further heated to 120 ° C. to distill off the residual monomer together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered and washed, and dried with a hot air drier at 50 ° C to obtain an ataryl polymer (p-1) having an average particle diameter of 350 / zm. The weight-average molecular weight of the obtained acryl-based polymer (p-1) was 200,000.

[Production Example 2] Production example of acrylic polymer (p_2)

After dissolving 435 parts of pure water and 1 part of polyvinyl alcohol (degree of saponification 88%, degree of polymerization 1000) in a reactor equipped with a cooling pipe, thermometer, stirrer, and nitrogen inlet pipe, methyl methacrylate 282 Part, methallylic acid 18 parts, octyl thioglycolate 0.39 part, and azobisisobutyronitrile 0.6 part were dissolved and a monomer solution was added thereto, and the mixture was stirred under a nitrogen atmosphere at 350 rpm. The temperature was raised to 70 ° C over a period of time, and heating was continued for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours, and further heated to 120 ° C. to distill off residual monomers together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered, washed, and dried with a hot air drier at 50 ° C. An acryl-based polymer (p-2) having a particle diameter of 350 μm was obtained. The weight average molecular weight of the obtained acrylyl-based polymer (P-2) was 200,000.

[Production Example 3] Production example of acrylic polymer (p-3)

After dissolving 435 parts of pure water and 1 part of polyvinyl alcohol (saponification degree: 88%, polymerization degree: 1000) in a reactor equipped with a cooling pipe, thermometer, stirrer, and nitrogen introduction pipe 29.5.5 parts of methyl methacrylate, 10.5 parts of methacrylic acid, 9 parts of octyl thioglycolate, and 0.6 parts of azobisisopuccil-tolyl The temperature was raised to 70 ° C. in 1 hour while stirring at 350 rpm, and heating was continued for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours, and further heated to 120 ° C. to distill off the remaining monomers together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered and washed, and then dried with a hot air drier at 50 ° C. to obtain an ataryl polymer (ρ−3) having an average particle size of 350 μΐη. The weight average molecular weight of the obtained acrylyl polymer (III-3) was 350,000.

[Production Example 4] Production example of acrylic polymer (ρ-4)

After dissolving 435 parts of pure water and 1 part of polyvinyl alcohol (saponification degree: 88%, polymerization degree: 1000) in a reactor equipped with a cooling pipe, thermometer, stirrer, and nitrogen introduction pipe Then, a monomer solution in which 300 parts of methyl methacrylate, 0.39 parts of octyl thioglycolate, and 0.6 parts of azobis isopyronitrile was dissolved was added, and the mixture was stirred at 350 rpm under a nitrogen atmosphere. The temperature was raised to 70 ° C in 1 hour with stirring, and the mixture was heated for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours. Then, the mixture was further heated to 120 ° C., and the remaining monomer was distilled off together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered and washed, and then dried with a hot air drier at 50 ° C. to obtain an acryl polymer (4-4) having an average particle diameter of 350 μτη. The weight average molecular weight of the obtained acrylic polymer (ρ-4) was 200,000.

[Production Example 5] Production example of ataryl polymer (A ρ-1).

In a reactor equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen introduction pipe, 435 parts of pure water and 1 part of Polyvinyl alcohol (saponification degree: 88%, polymerization degree: 1000) were dissolved. Thereafter, a monomer solution in which 1.91 parts of methyl methacrylate, 9 parts of methacrylic acid, 0.39 parts of octyl thioglycolate, and 0.6 parts of azobisisobutyronitrile were added was added. Then, in a nitrogen atmosphere, the temperature was raised to 70 ° C. in 1 hour while stirring at 350 rpm, and heating was continued for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours, and further heated to 120 ° C. to distill off residual monomers together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered and washed, and then dried with a hot air drier at 50 ° C to obtain an ataryl polymer (Ap-1) containing two or more lipoxyl groups in one molecule. The obtained acryl-based polymer (Ap_1) had a particle size of 350 µm and a weight-average molecular weight of 200,000.

[Production Example 6] Production example of ataryl polymer (B p-1)

After dissolving 435 parts of pure water and 1 part of Polyvinyl alcohol (saponification degree: 88%, polymerization degree: 1000) in a reactor equipped with a cooling pipe, thermometer, agitator, and nitrogen introduction pipe, methyl A monomer solution in which 234 parts of methacrylate, 66 parts of dimethylaminoethyl methacrylate, 3.0 parts of octyl thioglycolate, and 2 parts of azobisisobutyronitrile are charged is added. The temperature was raised to 70 ° C in 1 hour with stirring, and the mixture was heated for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours, and further heated to 120 ° C. to distill off residual monomers together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered and washed, and then dried with a hot air drier at 50 ° C to obtain an acrylic polymer (Bp-l) containing two or more amino groups in one molecule. The particle size of the obtained acrylyl polymer (Bp-l) was 350 m, and the weight average molecular weight was 50,000.

[Production Example 7] Production example of ataryl polymer (p-5)

In a reactor equipped with a cooling pipe, thermometer, stirrer, and nitrogen inlet pipe, 800 parts of pure water and 1 part of polyvinyl alcohol (88% saponification, 1000 degree of polymerization) were dissolved, and 400 parts of methyl methacrylate were dissolved. A monomer solution obtained by dissolving 3.8 parts of normal dodecyl mercaptan and 0.8 part of Azobisisosopuchi mouth-tolyl was added, and the mixture was heated to ° 0 ° C in 1 hour while stirring at 400 rpm under a nitrogen atmosphere. And heated for 2 hours. Thereafter, the temperature was raised to 90 ° C., and the mixture was heated for 2 hours. Then, the mixture was further heated to 120 ° C. to distill off residual monomers together with water to obtain a slurry, thereby completing the suspension polymerization. The obtained slurry was filtered and washed, and then dried with a hot air drier at 50 ° C. to obtain an acrylic polymer (p_5) having an average particle diameter of 100 // m. Weight of the obtained acrylic polymer (p-5) The average molecular weight was 40,000.

[Production Example 8] Production example of acrylic polymer (p-6)

Suspension polymerization was carried out in the same manner as in Production Example 7 except that the monomer solution to be charged was a monomer solution consisting of 400 parts of methyl methacrylate and 0.5 part of azobisisobutyronitrile. An acryl-based polymer (ρ-6) of 100 µm was obtained. The weight average molecular weight of the obtained acrylyl polymer (p-6) was 1.2 million.

[Production Example 9] Production example of acrylic polymer (p-7)

Same as Production Example 8 above, except that the monomer solution to be charged is a monomer solution consisting of 400 parts of methyl methacrylate, 0.52 parts of normal octaylmethyl.capbutane, and 0.4 parts of azobisisobutyronitrile. Suspension polymerization was carried out by the method described above to obtain an ataryl polymer (p-ke) having an average particle diameter of 100 zm. The weight average molecular weight of the obtained acrylyl-based polymer (p-7) was 150,000.

[Production Example 10] Production example of acrylic polymer (p-8)

Except that the monomer solution to be charged is a monomer solution comprising 400 parts of methyl methacrylate, 0.27 parts of normal dodecyl melcaptan, and 2 parts of azobisdisoptyronitrile, Suspension polymerization was performed in the same manner to obtain an ataryl polymer (p-8) having an average particle size of 100 μm. The weight average molecular weight of the obtained acrylyl polymer (ρ-8) was 300,000.

[Production Example 1 1] Production example of ataryl polymer (p-9)

A reactor equipped with a cooling pipe, a thermometer, a stirrer, a dropping device, and a nitrogen inlet pipe was charged with 925 parts by mass of pure water, sodium alkyldiphenyl ether disulfonate (Kao Corporation, trade name Perex SS-H ) 5 parts by mass and 1 part by mass of potassium persulfate were charged and heated to 70 ° C with stirring under a nitrogen atmosphere. A mixture of 500 parts by mass of methyl methacrylate and 5 parts by mass of sodium dialkylsulfosuccinate (trade name: Rex OT-P, manufactured by Kao Corporation) was added dropwise over 3 hours, and the mixture was kept for 1 hour. The emulsion polymerization was completed by raising the temperature to ° C and maintaining the temperature for 1 hour to obtain an emulsion having a polymer primary particle diameter of 0.08. The obtained emulsion is spray-dried using an Okawa Hara Koki Co., Ltd. L-8 spray-drying device to obtain secondary aggregate particles. An acryl-based polymer (Ρ-9), which is a non-crosslinked polymer powder having an average particle diameter of 30 μΐη and a weight average molecular weight of 600,000, was obtained.

The composition, weight average molecular weight (Mw), and presence or absence of a functional group of the acrylic polymer obtained in Production Examples 1 to 11 are shown in Table 1 below.

[Production Example 1 2] Production example of white stone pattern material

An acrylyl syrup was prepared by dissolving 29 parts of the acryl polymer (p-5) obtained in Production Example 7 in an ataryl monomer comprising 69 parts of methyl methacrylate and 2 parts of ethylene glycol dimethacrylate. To 100 parts of this acryl-based syrup, 2.0 parts of t-butyl peroxybenzoate (trade name "Perbutyl Z", manufactured by NOF Corporation) as a curing agent and 0.5 parts of stearic acid as an internal mold release agent After adding 0.25 parts of white inorganic pigment, 200 parts of aluminum hydroxide (manufactured by Showa Denko KK, trade name "Heidilite H_3 10") was added as an inorganic filler, and a production example was further used as a thickener. 30 parts of the acryl-based polymer (p-9) obtained in 11 was added and kneaded with a kneader for 10 minutes to obtain BMC. Next, this BMC is filled into a 200 mm square flat mold, heated and cured for 10 minutes at _a mold temperature of 130 ° C and a pressure of 1 OMPa to form a 1 Omm thick mold. Product was obtained. The obtained molded product was pulverized with a crusher and classified with a sieve to obtain a white stone-patterned material having an average particle diameter of 200 m. [Production Example 13] Production example of black stone pattern material

A black grain pattern material having an average particle diameter of 200 xm was obtained in the same manner as in Production Example 12, except that a black inorganic pigment was used instead of the white inorganic pigment.

[Example I-1]

Methyl methacrylate 22.4 parts, neopentyl glycol dimethacrylate 3.5 parts, polymerization inhibitor 2,6-di-t-butyl / butyl 4-methylphenol 0.01 part 5.6 parts of the powdery acryl-based polymer (P-1) obtained in Production Example 1 was dissolved in the mixture to prepare a syrup containing a polymer having a functional group that reacts with the inorganic filler, and then cured. 0.7 parts of t-amyl peroxybenzoate (manufactured by Kayaku Axo Co., Ltd., trade name "KD-1") and 0.1 part of zinc stearate as an internal mold release agent are added as an inorganic filler. Heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name “NS # 200”) 38.5 parts were mixed to prepare a mixture. At this time, the temperature of the mixture was 30 ° C., and the initial viscosity was 9.4 Pa · s (BH type viscometer, rotor rotation speed: 10 rpm).

70 parts of the mixture is applied to a thickness of 1 mm on two polypropylene release films, and a glass fiber roving of 13 μιη diameter (Asahi Fiberglass (Asahi Fiberglass) Co., Ltd., trade name “ER4630AF344”), cut to 25.4 mm, add 30 parts, overlay the surface coated with the other film mixture, and apply the mixture to the glass fiber. Impregnated. Next, this impregnated material was aged at 40 ° C. for 4 days to obtain SMC. This SMC had good film peelability, and the surface from which the film was peeled was slightly sticky, but there was no practical problem and the handleability was good. In addition, no impairment of impregnating property was observed in glass fibers contained in SMC, and impregnating property to glass fibers was good.

Next, the SMC from which this film was peeled was filled into a molding die, and heated at a temperature of 125 ° C for the upper die, a temperature of 115 ° C for the lower die, and a pressure of 10 MPa for 4 minutes. It was pressure cured to obtain a 4 mm thick, 200 mm square flat resin molded product. The obtained resin molded article had a good appearance. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, the color change was extremely small, and the hot water resistance was extremely good.

[Example I-1 2] SMC was obtained in the same manner as in Example 1 except that the powdery acrylic polymer (p-2) was used instead of the powdery acrylic polymer (p-1). . The temperature of the mixture was 30 ° C, and the initial viscosity was 25 Pa · s (BH type viscometer, rotor rotation speed: 10 rpm). The obtained SMC had good film release properties, had no tackiness on the surface after the film was peeled off, and had good handleability. Further, although impairment of impregnating property was slightly observed in the glass fiber contained in SMC, the impregnating property to glass fiber was good, which was a practically problematic level.

Next, the SMC from which this film was peeled was filled into a molding die, and heated and pressed for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of 1 OMPa. This was cured to obtain a flat resin molded product having a thickness of 4 mm and a size of 20 Omm square. The obtained resin molded article had a good appearance. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, the color change was extremely small, and the hot water resistance was extremely good.

[Example I-1 3]

In Preparation Example 1, a monomer mixture consisting of 22.4 parts of methyl methacrylate, 3 and 5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor was used. 5.6 parts of the obtained powdery acryl-based polymer (P-1) was dissolved to prepare a syrup containing a polymer having a functional group that reacts with an inorganic filler, and t-aminoleper was used as a curing agent. After adding 0 and 7 parts of oxybenzoate (KD-1) and 0.1 part of zinc stearate as an internal release agent, heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd.) as an inorganic filler 35.0 parts, light calcium carbonate (trade name, “Shiraishika CCR”, manufactured by Shiraishi Kogyo Co., Ltd.) 3.5 parts were mixed to prepare a mixture. At this time, the temperature of the mixture was 30 ° C., and the initial viscosity was 10.1 Pa · s (BH type viscometer, rotor rotation speed: 10 rpm).

70 parts of the mixture is applied to a thickness of 1 mm on two polypropylene release films, and a glass fiber roving (ER4630 AF) with a diameter of 13 μm is applied to the acryl-based premix coated surface of one of the films. 344) was cut to 25.4 mm, 30 parts of the mixture were added, and the surface of the other film coated with the mixture was overlaid to impregnate the glass fibers with the mixture. The impregnated material is then aged at 40 ° C for 4 days, SMC was obtained. This SMC had good film releasability, had no tackiness on the surface after the film was peeled off, and had good handleability. In addition, no impairment of the impregnating property was observed in the glass fibers contained in the SMC, and impregnating property on the glass fibers was good. Next, the SMC from which this film was peeled was filled into a molding die, and heated and pressed for 4 minutes under the conditions of an upper mold temperature of 125 ° C, a lower mold temperature of 115 ° C, and a pressure of OMPa. This was cured to obtain a 4 mm thick, 200 mm square flat resin molded product. The obtained resin molded article had a good appearance. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, the color change was extremely small, and the hot water resistance was extremely good.

[Example I-1 4]

In Preparation Example 4, a vinyl monomer mixture consisting of 16.2 parts of methyl methacrylate, 3.5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-tert-butyl 4-methyl phenol as a polymerization inhibitor was used. Dissolve 11.8 parts of the obtained powdery acryl-based polymer (P-4) to prepare a syrup containing a polymer having a functional group that reacts with the inorganic filler. After adding 0 and 7 parts of amyl peroxybenzoate (KD-1) and 0.1 part of zinc stearate as an internal mold release agent, heavy calcium carbonate (NS # 200) 38.5 as an inorganic filler And 0.08 part of magnesium oxide (Kyowa Mag 20 manufactured by Kyowa Chemical Industry Co., Ltd.) were mixed to prepare a mixture. At this time, the temperature of the mixture was 30 ° C., and the initial viscosity was 11.8 Pa · s (BH type viscometer, rotor rotation speed: 10 rpm).

· 'Apply the mixture to a thickness of 1 mm on two polypropylene release films, and apply a 13 Atm diameter glass fiber roving (E R4630 AF 344) on the acryl-based premix-coated surface of one of the films. ) Was cut into 25.4 mm, 30 parts were added, and the surface of the other film coated with the mixture was overlaid to impregnate the glass fiber with the mixture. Next, this impregnated material was aged at 40 ° C. for 4 days to obtain SMC. This SMC had good film peelability, had no stickiness on the surface after the film was peeled off, and had good handleability. No impairment of impregnating property was observed in the glass fibers contained in the SMC, and impregnating property on the glass fibers was good. Next, the SMC from which this film was peeled was filled into a molding die, and heated and pressed for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of 1 OMPa. Cured, A 4 mm thick, 200 mm square flat resin molded product was obtained. The obtained resin molded article had a good appearance. In addition, although slightly convex and blistering occurred on the surface of the molded product after immersion in hot water, the level was not a problem in practical use.

[Example I-1 5]

The powder obtained in Production Example 1 was added to a butyl monomer mixture comprising 28 parts of methyl methacrylate, 5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor. Acryl-based polymer (p-1) (12 parts) is dissolved to prepare a syrup containing a polymer having a functional group that reacts with an inorganic filler. T-Aminoleoxybenzoate (KD) is used as a curing agent. — 1) 0.7 parts, 0.1 part of zinc stearate as internal release agent, 0.25 parts of white or black inorganic pigment, heavy calcium carbonate (NS # 200) 55 as inorganic filler The part was put into a batch type kneader (Moriyama Seisakusho Co., Ltd., MS type double arm type kneader, G30-10 type) and kneaded for 10 minutes to obtain a mixture. Then, the mixture was sealed with a polyvinyl alcohol film and aged at 40 ° C. for 4 days to obtain BMC. This BMC had good film releasability, and although the surface from which the film was peeled had a slight stickiness, there was no practical problem and the handleability was good.

Next, the BMC from which this film was peeled was filled into a molding die, and cured by heating and pressing for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of OMPa. Then, a white or black resin molded product having a thickness of 4 mm and a thickness of 200 mm square was obtained. The obtained resin molded article had a good appearance. The surface of the molded article after immersion in hot water did not change, the color change was extremely small, and the hot water resistance was extremely good.

[Example I-1 6]

The white or black resin molded product obtained in Example I-15 was pulverized with a crusher to obtain a white or black grain pattern material having an average particle diameter of 350 / zm.

On the other hand, in Production Example 1, a vinyl monomer mixture comprising 22.4 parts of methyl methacrylate and 3.5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor was used. 5.6 parts of the obtained powdery acrylic polymer (P-1) is dissolved, and a syrup containing a polymer having a functional group that reacts with the inorganic filler is prepared. Milperoxibe After adding 0.7 parts of zonzoate (KD-1) and 0.1 parts by weight of zinc stearate as an internal mold release agent, 38.5 parts of heavy calcium carbonate (NS # 200) was obtained as an inorganic filler. A mixture was prepared by mixing 10 parts of a grain pattern material (5 parts of a white grain pattern material and 5 parts of a black grain pattern material). At this time, the temperature of the mixture was 30 ° C., and the initial viscosity was 15 Pa · s (BH type viscometer, rotor rotation speed: 1 O rpm).

Two polyproches. Apply the mixture to a thickness of 1 mm on a mold release film, and apply a glass fiber (ER4630AF 344) with a diameter of 13 μηη to 25.4 mm on the acryl-based premix coated surface of one of the films. The cut was cut, 20 parts of force D were applied, and the surface of the other film coated with the mixture was overlaid to impregnate the glass fiber with the mixture. Next! This impregnated material was aged at 40 ° C. for 4 hours to obtain SMC. This SMC had slight stickiness on the surface from which the film was peeled off, but there was no practical problem and the handleability was good. No impairment of impregnating property was observed in the glass fiber contained in SMC, and impregnating property to glass fiber was good.

Next, the SMC from which this film was peeled was filled in a molding die, and heated for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of 1 OMPa. It was pressure-cured to obtain a flat resin molded product having a thickness of 4 mm and a square of 20 Omm. The obtained resin molded article had a good appearance. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, the color change was extremely small, and the hot water resistance was extremely good. '

[Example I-I 7]

A vinyl monomer mixture consisting of 20 parts of methyl methacrylate and 5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor The powder obtained in Production Example 3 Dissolve 20 parts of the acrylic polymer (p-3) to prepare a syrup containing a polymer having a functional group that reacts with the inorganic filler, and use t-amyl peroxybenzoate (KD) as a curing agent. — 1) 0.7 parts, 0.1 part of zinc stearate as an internal mold release agent, 55 parts of heavy calcium carbonate (NS # 200) as an inorganic filler, and 0.1 part of magnesium oxide (Kyodmag 20) batch The mixture was charged into a formula kneader (Model G30-10) and kneaded for 10 minutes to obtain a mixture. Next, the mixture was sealed with a polyvinyl alcohol film and aged at 40 ° C. for 4 days to obtain BMC. This BMC is film peeling The film had good tackiness, had no stickiness on the surface after the film was peeled off, and had good handleability.

Next, the BMC from which this film was peeled was filled into a molding die, and heated and pressed for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of 1 OMPa. This was cured to obtain a flat resin molded product having a thickness of 4 mm and a size of 20 Omm square. The obtained resin molded article had a good appearance. In addition, although slightly convex and blistering occurred on the surface of the molded product after immersion in hot water, the level was not a problem in practical use.

[Comparative Example I-1]

A mixture was prepared in the same manner as in Example I-14, except that the amount of magnesium oxide (Kiyomag 20) was changed to 0.32 parts. At this time, the temperature of the mixture was 30 ° C., and the initial viscosity was 12.8 Pa · s (BH type viscometer, number of revolutions of rotor: 10 rpm). An SMC was produced in the same manner as in Example I-14, except that this mixture was used. This SMC had good film peelability, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, no impairment of impregnating property was observed in the glass fibers contained in the SMC, and impregnating property on the glass fibers was good. Further, a resin molded product was produced in the same manner as in Example I-4 except that this SMC was used. The obtained resin molded article had a good appearance. However, the surface of the molded product after hot water immersion had convexities and blisters, and the appearance was extremely poor, and the hot water was extremely poor.

[Comparative Example I-1 2]

The SMC was prepared in the same manner as in Example 1 except that the powdery acryl polymer (p-4) was used instead of the powdery acrylic polymer (P-1) as the polymer powder. Obtained. The temperature of the mixture was 30 ^DC , and the initial viscosity was 8.9 Pa · s (BH type viscometer, rotor rotation speed: 10 rpm). The resulting SMC was not thickened, had poor film release properties, had a sticky surface after the film was peeled off, and had poor handleability.

[Comparative Example I-3]

20 parts of methinore methacrylate and 5 parts of neopentylglyconoresin methacrylate, 2,6-di-tert-butyl 4-methylphenol as polymerization inhibitor 0.01 Dissolve 20 parts of the powdery acryl-based polymer (p-3) obtained in Production Example 3 into a butyl-based monomer mixture consisting of 3 parts by weight and contain a polymer having a functional group that reacts with an inorganic filler. Mix syrup, 0.7 parts of t-amyl peroxybenzoate (KD-1) as a hardener, 0.1 part of zinc stearate as an internal mold release agent, and heavy calcium carbonate (NS #) as an inorganic filler 200) 55 parts and 0.36 parts of magnesium oxide (Kyodmag 20) were put into a batch-type soda (G30-10 type) and kneaded for 10 minutes to obtain BMC. Next, the BMC was sealed with a polyvinyl alcohol film and aged at 40 ° C. for 4 days. This BMC had good film peelability, had no stickiness on the surface after the film was peeled off, and had good handleability. Next, the BMC from which this film was peeled was filled into a molding die, and cured by heating and pressing for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of OMPa. Then, a 4 mm thick, 20 Omm square flat resin molded product was obtained. The obtained resin molded article had a good appearance. In addition, protrusions and blisters were generated on the surface of the molded product after immersion in hot water, and the appearance of the tatto was extremely poor and the hot water was extremely poor.

The amounts of the components used in Examples I-11 to I-17 and Comparative Examples I11 to I-13 are summarized in Table I-11, and the evaluation results are shown in Table I-11. Figure 2 shows.

Table I

The abbreviations in Table I-11 are as follows.

MMA: Methyl methacrylate NPG: Neo. Cinnoleglycol / resin methacrylate NS # 200: Heavy calcium carbonate (Nitto Powder Chemical Co., Ltd., product name "NS # 200") White huahua CCR _: Light calcium carbonate (Shiroishi Kogyo Co., Ltd.) ), Brand name "white glamor CCR")

Table I-1 2

[Example II-1]

Methyl methacrylate I, 33 parts, neopentyl dimethyl dimethacrylate 5 parts, and 26-di-t-butyl-4-methylphenol (polymerization inhibitor) 0.0 1 part In a monomer mixture, 7 parts of the acryl polymer (Ap-1) obtained in Production Example 5 was dissolved, and a syrup (SA-1) containing a polymer having two or more carboxyl groups in one molecule was prepared. ) Was prepared.

45 parts of this syrup (SA-1), 0.7 parts of tamyl peroxybenzoxide (KD-1) as a curing agent, 0.1 part of zinc stearate as an internal mold release agent, 55 parts of heavy calcium carbonate (NS # 200) as filler and 0.07 parts of hexamethylenediamine as compound (Bm) having two amino groups in one molecule The mixture was kneaded with a kneader (G30-10 type) for 10 minutes to obtain a mixture. Then, the mixture was sealed with a polyvinyl alcohol film and aged at 40 ° C. for 4 days to obtain BMC. This BMC had good film releasability and a slight stickiness on the surface from which the film was peeled off, but there was no practical problem and the handleability was good.

Next, the BMC from which this film was peeled was filled into a molding die, and heated and pressed for 4 minutes under the conditions of an upper die temperature of 125 ° C, a lower die temperature of 115 ° C, and a pressure of 10 MPa. After curing, a flat resin molded product having a thickness of 4 mm and a square of 200 mm was obtained. Molding of the obtained resin molded product The appearance of the product was good. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, and there was a slight change in color.

[Example II-2]

To a vinyl monomer consisting of 89 parts of methyl methacrylate and 0.04 part of 2,6-di-t-butyl-4-methylphenol, 111 parts of the acryl-based polymer (Bp-1) obtained in Production Example 6 was added. After dissolution, a syrup (SB-1) containing a polymer containing two or more amino groups in one molecule was prepared.

Example 45 To 45 parts of the syrup (SA-1) prepared in Example 1, 0.7 parts of t-milperoxybenzoate as a curing agent, 0.1 part of zinc stearate as an internal release agent, and an inorganic filler And 55 parts of heavy calcium carbonate and 4.7 parts of syrup (SB_1) were added and kneaded for 10 minutes by a batch method to obtain a mixture. Then, the mixture was sealed with a polyvinyl alcohol film and aged at 40 ° C. for 4 days to obtain BMC. This BMC had good film peelability, and the surface from which the film was peeled was slightly sticky. However, there was no practical problem and the handling and the properties were good.

Next, the BMC from which the film was peeled was filled in a molding die, and a resin molded product was obtained in the same manner as in Example II-1. The appearance of the obtained resin molded product was good. Further, the surface of the molded article after immersion in hot water was not convex or blistering was observed, and there was slight color change. However, the level was not a problem in practical use, and the hot water resistance was good.

[Example III-3]

Production example of vinyl monomer mixture consisting of 25.2 parts of methyl methacrylate, 3.5 parts of neopentynoleglycol dimethacrylate, and 0.01 part of 2,6-di-tert-butyl-4-methylphenol 0.01 parts 2. · 8 parts of the acrylic polymer (Ap-1) obtained in the above was dissolved to prepare a syrup (SA-2) containing a polymer having two or more carboxyl groups in one molecule.

31.5 parts of this syrup (SA-2), 0.7 parts of t-amyl peroxybenzoate as a hardening agent, 0.1 part of zinc stearate as an internal mold release agent, and heavy as an inorganic filler Calcium carbonate 38.5 parts, syrup prepared in Example II-2 (SB-1) 1.9 parts were added and mixed to prepare a mixture. At this time, the temperature of the mixture was 30 ° C, and the initial viscosity was 7.5 Pa · s.

70 parts of the mixture is applied to a thickness of 1 mm on two polypropylene release films, and a glass fiber roving (E R4630 AF 344) with a diameter of 13 / m is applied to the surface of the one film where the mixture is applied. The mixture was cut into 25.4 mm, 30 parts were added, and the surface of the other film coated with the mixture was overlaid to impregnate the glass fiber with the mixture. Next, the impregnated material was aged at 40 ° C. for 4 days to obtain SMC. This SMC had good film releasability, and although the surface from which the film was peeled off was slightly sticky, there was no practical problem and the handleability was good. In addition, the impregnation property of the glass fiber was good.

Next, SMC from which the film was peeled was filled in a molding die, and a resin molded product was obtained in the same manner as in Example II-1. The appearance of the obtained resin molded product was good. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, and there was slight color change. However, it was a practically problematic level, and the hot water resistance was good.

[Example II-4]

The polymer obtained in Production Example 5 was added to a vinyl monomer mixture consisting of 24.5 parts of methyl methacrylate, 3.5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-tert-butyl-4-methylphenol. (Ap-1) 3.5 parts were dissolved to prepare a syrup (SA-3) containing a polymer having two or more carboxyl groups in one molecule.

31.5 parts of this syrup (SA-3), 0.7 parts of t-amyl peroxy t-amyl peroxy benzoate as a curing agent, 0.1 part of zinc stearate as an internal mold release agent, and heavy as an inorganic filler 38.5 parts of calcium carbonate and 0.84 parts of syrup (SB-1) prepared in Example I-2 were added and mixed to prepare a mixture. At this time, the temperature of the mixture was 30 ° C, and the initial viscosity was 5.4 Pa · s.

Using this mixture, a glass fiber was impregnated with the mixture in the same manner as in Example III-3, followed by aging to obtain SMC. This SMC had good film releasability and a slight stickiness on the surface from which the film was peeled off, but there was no practical problem and the handleability was good. In addition, the impregnation into glass fibers was also good. Next, the SMC from which the film was peeled was filled in a molding die, and a resin molded product was obtained in the same manner as in Example II-1. The appearance of the obtained resin molded product was good. Also, no protrusions or blisters were observed on the surface of the molded product after immersion in hot water, and there was slight color change. However, it was a practically problematic level, and the hot water resistance was good.

[Comparative Example Π— 1]

A vinyl monomer mixture consisting of 23.1 parts of methyl methacrylate, 3.5 parts of neopentyl glycol dimethacrylate, and 0.01 part of 2,6-di-t_butyl-41-methylphenol was obtained in Production Example 5 in Preparation Example 5. Acrylic polymer (Ap-1) 4. 9 parts were dissolved to prepare a syrup (SA-4) containing a polymer having two or more carboxyl groups in one molecule.

45 parts of this syrup (SA-4), 0.7 parts of tamyl peroxybenzolate as a hardener, 0.1 part of zinc stearate as an internal mold release agent, and heavy calcium carbonate as an inorganic filler 55 parts and 1 part of magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) as a thickener were added and kneaded with a batch kneader for 10 minutes to obtain BMC. The BMC was then sealed with a polyvinyl alcohol film. Aged for 4 days at C. This BMC had good film peelability, had no stickiness on the surface after the film was peeled off, and had good handleability. Next, the BMC from which the film was peeled was filled in a molding die, and a resin molded product was obtained in the same manner as in Example II-1. The appearance of the obtained resin molded product was good. However, protrusions and blisters were generated on the surface of the molded product after immersion in hot water, and the appearance was extremely poor, and the hot water was extremely poor.

[Comparative Example II-2]

Comparative Example シ -.1 syrup (SA-4) 31.5 parts prepared, 0.7 part of t-amyl peroxybenzoate as a curing agent, 0.1 part of zinc stearate as an internal mold release agent Then, 38.5 parts of heavy calcium carbonate as an inorganic filler and 0.7 parts of magnesium oxide (Kyowa Mag 20) as a thickener were added and mixed to prepare a mixture. At this time, the temperature of the mixture was 30 ° C., and the initial viscosity was 5 Pa · s.

Using this mixture, a glass fiber was impregnated with the mixture in the same manner as in Example III-3, followed by aging to obtain SMC. This SMC has good film peelability and / After the REM has been peeled off, there is no stickiness on the surface. /, The properties were good. In addition, the impregnation property of the glass fiber was good.

Next, the SMC from which the film was peeled was filled in a molding die, and a resin molded product was obtained in the same manner as in Example II-1. The appearance of the obtained resin molded product was good. However, the surface of the molded article after immersion in hot water had convexity and phthalation, and the appearance was extremely poor, and the hot water was extremely poor.

Example II-1 to Example II-4 and Comparative Example II-1 to Comparative Example II-2 show the composition of the prepared syrup as summarized in Table III-1 below, and the composition and evaluation of the mixture. The results are shown in Table II-2 below.

Table Π— 1

The abbreviations in Table II-1 are as follows.

MM A methyl methacrylate

N P G Neopentinole glycol dimethacrylate

BHT 2, 6-G

Table Π— 2

The abbreviations in the table are as follows.

HMD: Hexamethylene diamine

NS # 200: Heavy calcium carbonate (manufactured by Nitto Powder Industries Co., Ltd., trade name NS # 200)

[Example m-l] (Viscosity due to physical dissolution)

Methyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acryster M")

9. 9 parts and neopentyl glycol dimethacrylate (Shin-Nakamura Chemical Co., Ltd., trade name "NK ester NPG") 21.3 Acrylic monomer (m) consisting of 3 parts and polymer powder (p-5) 5. Acrylic syrup in which 7 parts are dissolved, calcium carbonate (Nitto Powder Chemical Co., Ltd., trade name NS # 200) as an inorganic filler (F) 59,6 咅 [5. 0.59 parts of W996 (trade name, manufactured by Big Chemie Japan KK) and 0.115 parts of zinc stearate as an internal mold release agent were mixed. To this mixture, 0.7 part of t-amyl peroxybenzoate (KD-1) is used as a curing agent (Z), and 2.8 parts of a powdered acryl-based polymer (p-6) is used as a thickener. And an acryl-based monomer (m), an acrylic polymer (p), an inorganic filler (F), and other additives. An acrylic premix comprising the curing agent (Z) was prepared. At this time, the temperature of the acryl-based premix was 30 ° C, and the viscosity immediately after the addition of the thickener was 12 Pa · s (BH type viscometer, number of rotations of the rotor: 20 rpm). Was.

Separately, a composition was prepared by removing the curing agent from this acrylic premix, and prepared in the same manner as described above, and aged at 40 ° C for 3 days to increase the viscosity to obtain an acrylic resin composition (X). Was. The dynamic viscoelasticity of this acrylic resin composition (X) at 20 to 80 ° C. was measured, and taηδ was measured. The results of the evaluation of tan 6 at typical temperatures of 20 to 80 ° C are shown in Table DI-2.

On two polypropylene release films, apply 100 parts of the acryl-based premix immediately after addition of the thickener described above to a thickness of 1 mm, and apply the acryl-based premittus of one of the films to the As a fiber reinforcing agent (Y), a 13 μm diameter glass fiber roving (manufactured by Asahi Fiber One Glass Co., Ltd., trade name “ER4800 LBAF 21 OWJ”) is cut into 25.4 mm, 42.6 parts of calorie were added, and the surface of the other film coated with the acryl-based premix was overlapped, and the glass fiber was impregnated with the acryl-based premix. After aging for 3 days at 40, an SMC consisting of 100 parts of an acryl-based resin composition (X), 42.6 parts of a fiber reinforcing agent (Y), and 0.7 parts of a curing agent (Z) was obtained. Has good film release properties, There was no stickiness on the surface after the film was peeled off, and the handleability was good. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, indicating that the impregnation into the glass fiber was good.

Next, the SMC from which this film was peeled was charged into a molding die, and heated for 4 minutes under the conditions of an upper die temperature of 140 ° C, a lower die temperature of 125 ° C, and a pressure of 10 MPa. It was pressure-cured to obtain a deep drawn bus tap-shaped ataryl-based resin molded product having a thickness of 6 mm, a length of 200 mm, a width of 250 mm, a depth of 100 mm and a thickness of 6 mm. There was no underfill in the obtained resin molded product. In addition, although the surface of the obtained molded article had a small number of irregularities of the glass fiber, it had a practically problematic appearance.

[Example m-2] (Thickening by physical dissolution)

5.0 parts of a powdery acryl-based polymer (p-5) was dissolved in 4.9 parts of methyl methacrylate and 5.0 parts of an antaryl monomer (m) consisting of 5.0 parts of neopentyl glycol dimethacrylate. 54.6 parts of carbonated calcium carbonate as inorganic filler (F), 0.595 parts of W996 as a viscosity reducing agent, and 0.5 parts of zinc stearate as an internal mold release agent. 15 parts were mixed. To this mixture, 0.7 part of t-amyl peroxybenzoate as a curing agent (Z) and 19.8 parts of a polymer powder (p-5) as a thickener were added and mixed. Acrylic premix composed of acrylic resin composition (X) consisting of monomer (m), acrylic polymer (p), inorganic filler (F), and other additives, and curing agent (Z) did. At this time, the temperature of the acrylic premix was 30 ° C., and the viscosity immediately after the addition of the viscosity agent was 8 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm).

Separately, a composition was prepared by removing the curing agent from the acrylic premix, prepared in the same manner as described above, and aged at 40 ° C for 3 days to increase the viscosity to obtain the ataryl resin composition (X). Obtained. The dynamic viscoelasticity of this acrylic resin composition (X) at 20 to 80 ° C. was measured, and taηδ was measured. Table II-2 shows the evaluation results of taηδ at typical temperatures of 20 to 80 ° C.

Using the acryl-based premix immediately after adding the thickener, impregnating the glass fibers in the same manner as in Example IE-1, aging the impregnated material at 40 ° C for 3 days, 100 parts of resin composition (X), 42.6 parts of fiber reinforcing agent (Y), and 0.02 parts of curing agent (Z). SMC consisting of 7 parts was obtained. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. When the film was peeled off, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, a bathtub-shaped acryl-based resin molded product was obtained in the same manner as in Example II-1, using the SMC from which the film was peeled off. There was no underfill in the obtained resin molded product. In addition, the surface of the resin molded product had no irregularities of the glass fiber, and the appearance was extremely good.

[Example m-3] (Thickening by chemical reaction)

To an acrylic syrup prepared by dissolving 16.7 parts of the polymer powder (P-3) in an acrylic monomer (m) consisting of 23.2 parts of methyl methacrylate and 5.0 parts of neopentylglycol dimethacrylate, 54.85 parts of calcium carbonate as an inorganic filler (F) and 0.14 parts of zinc stearate as an internal release agent were mixed. To this mixture was added 0.7 parts of t-amyl peroxybenzoate as a curing agent (Z) and magnesium oxide as a thickening agent (Kyowa Mag 20 manufactured by Kyowa Chemical Industry Co., Ltd.). And an acrylic resin composition (X) comprising an acrylic monomer (m), an acrylic polymer (P), an inorganic filler (F), and other additives, and a curing agent. An acrylic premix consisting of (Z) was prepared. At this time, the temperature of the acryl-based premix was 30 ° C, and the viscosity immediately after the addition of the thickener was 12 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm).

Separately, a composition was prepared by removing the curing agent from this acrylic premix, blended in the same manner as above, and aged at 40 ° C for 3 days to thicken the acrylic resin composition (X). Obtained. The dynamic viscoelasticity of this acrylic resin composition (X) at 20 to 80 ° C. was measured, and t an <5 was measured. Table II-2 shows the evaluation results of ta η δ at typical temperatures of 20 to 80 ° C.

ガラス Using the acryl-based premix immediately after the addition of the viscosity agent, impregnate the glass fiber in the same manner as in Example IE-1, and aged this impregnated material at 40 ° C for 3 hours. An SMC comprising 100 parts of the composition (X), 42.7 parts of the fiber reinforcing agent (Y), and 0.7 part of the curing agent (Z) was obtained. This SMC has good film release properties, There was no stickiness on the surface after peeling, and the handleability was good. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, using the SMC from which the film was peeled off, a passtab-shaped acryl-based resin molded product was obtained in the same manner as in Example II-1. There was no underfill in the obtained resin molded product. In addition, the surface of the resin molded product had almost no irregularities of the glass fiber, and the appearance was good.

[Comparative Example II-1] (Thickening by chemical reaction)

As the component (m), an attaryl monomer consisting of 32.9 parts of methyl methacrylate and 5.0 parts of neopentylglycol dimethacrylate was used, and as the component (p), a powdery acrylic polymer was used. (P-1) An acrylic premix was prepared in the same manner as in Example m-13 except that 7.0 parts was used, and the temperature of the acrylic premix at this time was 30 ° C. The viscosity immediately after the addition of the adhesive was 5 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm).

Separately, a composition was prepared by removing the curing agent from this acrylic premix in the same manner as described above, and the mixture was aged at 40 ° C for 3 days to increase the viscosity to obtain an acrylic resin composition (X). Obtained. The dynamic viscoelasticity of this acrylic resin composition (X) at 20 to 80 ° C. was measured, and taηδ was measured. Table II-2 shows the evaluation results of taηδ at typical temperatures of 20 to 80 ° C.

ガラス Using the acryl-based premix immediately after the addition of the thickener, impregnate the glass fiber in the same manner as in Example II-11, ripening the impregnated material at 40 ° C for 3 days, 100 parts of resin composition (X), 42.7 parts of fiber reinforcing agent (Y), and 0.02 parts of curing agent (Z).

I got a 7 part SMC. This SMC had good film releasability, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, an acrylic resin molded article having a bathtub shape was obtained in the same manner as in Example IE-1, using the SMC from which the film was peeled off. However, the obtained resin molded product had underfill, and the glass fiber had large irregularities, and the appearance was poor. Table HI-1 shows the compositions of the prepared acryl-based resin compositions for Examples in-l to Examples m_3 and Comparative examples in-l, and representative temperatures of 20 to 80 ° C. The evaluation results of ta η δ in Table HI-2 are shown below.

Table m—

O

The abbreviations in the table are as follows.

MM A: Methyl methacrylate

N P G: Neo pliers / reglycolate

NS # 200: Heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name NS # 200)

Table m—2

[Example IV-1]

Methyl methacrylate (acrylic ester M) 1 2 parts of neopentylglycol / resinmethacrylate (NK ester NPG) 4 parts of acrylic monomer (m), 0.44 parts of thinning agent W 996, After adding 0.1 part of zinc stearate as an internal release agent, 44 parts of calcium carbonate (trade name: NS # 200, manufactured by Nitto Powder Chemical Co., Ltd.) is mixed as an inorganic filler (F) to form an acrylic resin. A mixture consisting of the system monomer (m), the inorganic filler (F), and other additives was prepared. To this mixture was added 0.7 part of tamyl peroxybenzoate (KD-1) as a curing agent (Z), and the powdery acrylic polymer (P-5) obtained in Production Example 7 as a thickener. ) 20 parts were added and mixed, and an ataryl resin composition (X) comprising an acrylic monomer (m), an inorganic filler (F), a thickener, and other additives, and a curing agent ( Z) was mixed with an acrylic premix. At this time, the temperature of the acryl premise was 30 ° C., and the viscosity immediately after the addition of the thickener was 7.2 Pa · s (BH type viscometer, rotation speed of rotor: 20 rpm).

Separately, a composition was prepared by removing the curing agent from the acrylic premix in the same manner as described above, and the mixture was aged at 40 ^DC for 3 days to increase the viscosity to obtain an acrylic resin composition (X). Was. The complex viscosity at 30 ° C. of the acryl-based resin composition (X) is 5 × 10 ⁴ Pa's, and 80. Complex viscosity in C, 7 X 10 ² double in P a * s (30 ° C (0.01 times the original viscosity).

The above-mentioned thickener and the acryl-based premix immediately after addition were applied to a thickness of 1 mm on two polypropylene release films, and the diameter of the acryl-based premix of one film was reduced to 13 mm. / m glass fiber roving (ER4800 LB AF 210W) is cut to 25.4mm, 20 parts are added, and the other film is coated with the acryl-based premittas coated surface. An acrylic premix was impregnated. Next, this impregnated material was aged at 40 ° C. for 3 days to obtain SMC. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, the SMC from which this film was peeled was charged into a molding die, and heated and cured under heat and pressure for 4 minutes at an upper mold temperature of 140 ° C, a lower mold temperature of 125 ° C, and a pressure of 1 OMPa. A 6 mm thick, 200 mm long, 250 mm wide, 10 Omm deep, 6 mm thick deep drawn bathtub-shaped acrylic resin molded product was obtained. There was no underfill in the obtained resin molded product, and there was no defect due to bubbles on the surface, and the appearance was very good. The bending strength of the obtained molded product was 130 MPa.

[Example IV-2]

In the same manner as in Example IV-1, except that the amount of neopentyl diol dimethacrylate added was changed to 5.6 parts and that 18.4 parts of the polymer powder (p-7) was used as a thickener, Acryl premix was prepared. At this time, the temperature of the acryl-based premix was 30 ° C, and the viscosity immediately after the addition of the thickener was 6 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm).

Further, similarly to Example IV-1, separately, a composition was prepared by removing the curing agent from this acryl-based premix, and the mixture was aged and thickened to obtain an acrylic resin composition. The complex viscosity at 30 ° C. of this ataryl resin composition was 5 × 10 ⁴ Pa.s, and the complex viscosity at 80 ° C. was 7 × 10 ³ Pa.s (complex viscosity at 30 ° C.). (0.14 times the viscosity).

方 Same as in Example IV-1 using the acrylic premix immediately after adding the thickener By the method, SMC was obtained. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, using the SMC from which the film was peeled off, a bathtub-shaped acrylic resin molded product was obtained in the same manner as in Example IV-1. There was no underfill in the obtained resin molded product. In addition, the surface of the resin molded product, when viewed closely, had only a few defects due to air bubbles, but had practically no problem and had good appearance. The bending strength of the obtained molded product was 130 MPa.

[Example IV-3]

The addition amount of methyl methacrylate to 10.5 parts, the addition amount of neopentyl glycol dimethacrylate to 3.5 parts, the addition amount of inorganic filler to 38.5 parts, and the addition amount of thickener W996 An ataryl-based premix was prepared in the same manner as in Example IV-1 except that the addition amount of the polymer powder (P-5) was changed to 0.35 parts and the amount of the polymer powder (P-5) was changed to 17.5 parts. . At this time, the temperature of the ataryl-based premix was 30 ° C, and the viscosity immediately after adding the thickener was 7.2 Pa · s (BH type viscometer, rotation speed of a single mouth: 20 rpm). Further, similarly to Example IV-1, an acrylic resin composition was separately prepared with a composition obtained by removing the curing agent from the acrylic premix, and the mixture was aged and thickened to obtain an acrylic resin composition. The complex viscosity of this acryl-based resin yarn at 30 ° C is 5 × 10 ⁴ Pa's, and the complex viscosity at 80 ° C is 7 × 10 ² Pas (at 30 ° C). 0.01 times the complex viscosity of

S SMC was obtained in the same manner as in Example IV-1, except that the addition amount of the glass fiber was changed to 30 parts using the acryl-based premix immediately after the addition of the viscosity agent. This SMC had good film release properties, had no tackiness on the surface after the film was peeled off, and was handled well. Further, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, using the SMC from which this film was peeled off, a passtab-shaped acrylic resin molded product was obtained in the same manner as in Example IV-1. There was no underfill in the obtained resin molded product, and there was no defect due to air bubbles on the surface, and the appearance was very good. Also get The bending strength of the molded product was 18 OMPa.

[Example IV-4]

In place of the component (a), as the component (S), 6 parts of a polymer powder (p-5) were dissolved in an acryl-based monomer composed of 12 parts of methyl methacrylate and 4 parts of neopentyl glycol dimethacrylate. A method similar to that of Example IV-1 was used except that the amount of the powdery acrylic polymer (P-5) used as a thickener was changed to 14 parts using an acrylic syrup. An acrylic premix was prepared. At this time, the temperature of the ataryl-based premix was 30 ° C, and the viscosity immediately after the addition of the viscosity agent was 15 Pa's (BH type viscometer, rotor rotation speed: 20 rpm).

Further, similarly to Example IV-1, an acrylic resin composition was separately prepared with a composition obtained by removing the curing agent from the acrylic premittas, aged, and thickened to obtain an acrylic resin composition. The complex viscosity of this acryl-based resin composition at 30 ° C is 5 × 10 ⁴ Pa · s, and the complex viscosity at 80 ° C is 7 × 10 ² Pa · s (complex viscosity at 30 ° C). (0.01 times the viscosity).

An SMC was obtained in the same manner as in Example IV-1, except that the amount of glass fiber added was changed to ³⁰ parts using the acrylic premix immediately after the addition of the thickener. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. Further, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation property into the glass fiber was good.

Next, a bathtub-shaped acryl-based resin molded product was obtained in the same manner as in Example IV-1, using the SMC from which the film was peeled off. There was no underfill in the obtained resin molded product, and there was no defect due to air bubbles on the surface, and the appearance was very good. The bending strength of the obtained molded product was 13 OMPa.

[Example IV-5]

· In the same manner as in Example IV-1, except that the amount of neopentyl alcohol dimethacrylate was changed to 2 parts and the amount of the polymer powder (p-5) was changed to 22 parts, Acryl premix was prepared. At this time, the temperature of the acrylic / mix premix was 30 ° C, and the viscosity immediately after adding the thickener was 28 Pa · s (BH type viscometer, rotor rotation speed: 10 rϋm). . Further, similarly to Example I-1, an acrylic resin composition was separately prepared with a composition obtained by removing the curing agent from the acryl-based premittas, and aged to increase the viscosity. The complex viscosity at 30 ° C. of this ataryl resin composition is 1.5 × 10 ⁵ Pas, and the complex viscosity at 80 ° C. is 3 × 10 ³ Pas (30 ° C. 0.02 times of the complex viscosity at).

An SMC was obtained in the same manner as in Example IV-1, using the acryl-based premix immediately after the addition of the thickener. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, using the SMC from which the film was peeled off, a bus tap-shaped ataryl-based resin molded product was obtained in the same manner as in Example IV-1. There was no underfill in the obtained resin molded product, and there was no defect due to air bubbles on the surface, and the appearance was very good. The bending strength of the obtained molded product was 130 MPa.

[Example IV-6]

Except that the amount of neopentyl glycol dimethacrylate added was changed to 8 parts and the amount of polymer powder (p-5) was changed to 16 parts, an acrylic prepolymer was prepared in the same manner as in Example IV-1. Mix was mixed. At this time, the temperature of the acryl-based premix was 30 ° C, and the viscosity immediately after the addition of the viscosity agent was 5 Pa · s (BH type viscometer, number of rotations of the rotor: 20 rpm).

Further, similarly to Example IV-1, an acrylic resin composition was separately prepared with a composition obtained by removing the curing agent from the acryl-based premittas, and then aged to increase the viscosity. The complex viscosity at 30 ° C for Atariru resin composition is ^{4 · 5 X 10 3 P a} · s, the complex viscosity at 8 0 ° C, 1. 2 X 10 2 P a 's (30 ° C of the complex viscosity at ° C).

S SMC was obtained in the same manner as in Example IV-1, using the acryl-based premix immediately after the addition of the thickener. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good. Met.

Next, using the SMC from which the film was peeled off, an acryl-based resin molded article having a bathtub shape was obtained in the same manner as in Example IV-1. There was no underfill in the obtained resin molded product. In addition, the surface of the M-shaped molded product, when viewed closely, had very few defects due to air bubbles, but had practically no problem and had good appearance. The bending strength of the obtained molded product was 130 MPa.

[Example IV-7]

Methyl methacrylate 9. Acrylic syrup (S) prepared by dissolving 3.4 parts of powdery acryl-based polymer (P-5) in acryl-based monomer consisting of 2 parts and 10 parts of neopentyl glycol dimethacrylate ) And 0.1 part of zinc stearate as an internal mold release agent, and then as an inorganic filler (F) 3 9 parts of aluminum hydroxide (BW-33ST, manufactured by Nippon Light Metal Co., Ltd.) Then, 6 parts of the white inorganic filler-containing resin particles obtained in Production Example 12 as the stone pattern material (W) and 6 parts of the black inorganic filler-containing resin particles obtained in Production Example 13 were mixed. A mixture consisting of acrylic syrup (S), inorganic filler (F), stonework material (W), and other additives was prepared.

To this mixture was added 0.7 part of t-amylpropoxybenzoate as a curing agent (Z), and 6.4 parts of a powdery acryl-based polymer (P-6) obtained in Production Example 8 as a thickener. Is added and mixed, and an ataryl resin composition (X) comprising an acrylic monomer (S), an inorganic filler (F), a thickener, a stone pattern material (W), and other additives An acrylic premix consisting of a curing agent (Z) was prepared. At this time, the temperature of the acrylic premix was 30 ° C, and the viscosity immediately after adding the thickener was 4.3 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm). Was.

Separately, a composition was prepared by removing the curing agent from the acrylic premix in the same manner as above, and the mixture was aged at 40 ° C for 3 days to obtain a acryl-based resin composition (X). Was. The complex viscosity at 3 0 ° C of the acrylic resin composition (X) is ^{4 X 1 0 4 P a.} S, the complex viscosity at 80 ° C, l X 1 0 2 P a. S ( It was 0.0025 times the complex viscosity at 30 ° C).

An SMC was obtained in the same manner as in Example IV-1, using the acryl-based premix immediately after the addition of the thickener. This SMC has good film release properties and peels off the film The surface after the coating had no tackiness and the handleability was good. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, using the SMC from which this film was peeled off, a bathtub-shaped granite-like acrylic resin molded product was obtained in the same manner as in Example IV-1. There was no underfill in the obtained resin molded product, and there was no defect due to bubbles on the surface, and the appearance was very good. The bending strength of the obtained molded product was 130 MPa.

[Comparative Example IV-1]

The amount of neopentylglycol / resin methacrylate was changed to 10.4 parts, and 13.6 parts of the polymer powder (p-8) was used as a thickener. An acryl premix was prepared in the same manner as. At this time, the temperature of the acrylic premix was 30 ° C, and the viscosity immediately after the addition of the viscosity agent was 4.5 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm).

Further, similarly to Example 1V_1, an acrylic resin composition was separately prepared with a composition obtained by removing the curing agent from the acryl-based premittas, and aged to increase the viscosity. The complex viscosity at 3 0 ° C for Atariru resin composition is ^{5 X 1 0 4 P a ·} s, the complex viscosity at 8 0 ° C ^{is, 2 X 1 0 4 P a} · s (3 0 (0 · 4 times the complex viscosity at C). An SMC was obtained in the same manner as in Example IV-1, using the acryl-based premix immediately after the addition of the thickener. This SMC had good film release properties, had no stickiness on the surface after the film was peeled off, and had good handleability. In addition, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation into the glass fiber was good.

Next, a bathtub-shaped molded product was obtained in the same manner as in Example IV-1 using the SMC from which this film was peeled. The obtained molded article had underfill, and also had defects on the surface due to bubbles, and the appearance was poor.

[Comparative Example IV-2]

A method similar to that of Example IV-1 was used, except that the amount of neopentyl glycol dimethacrylate was changed to 12 parts and the amount of polymer powder (ρ_5) was changed to 12 parts. An acrylic premix was prepared. Acrylic premix at this time Was 30 ° C., and the viscosity immediately after the addition of the thickener was 4 Pa · s (BH type viscometer, rotor rotation speed: 20 rpm).

Further, similarly to Example IV-1, separately, a composition was prepared by removing the curing agent from this acryl-based premix, and the mixture was aged and thickened to obtain an acrylic resin composition. Complex viscosity at 3 0 ° C in this Atariru resin composition is ^{3 X 1 0 2 P a ·} s, the complex viscosity at 8 0 ° C ^{is, 4 X 1 0 1 P a} · s (3 0 (0.13 times the complex viscosity at ° C).

SSMC was obtained in the same manner as in Example IV-1 using the acryl-based premix immediately after the addition of the thickener. This SMC had poor film releasability, had a sticky surface after the film was peeled off, and had poor handleability. Further, when the film was peeled, no peeling was observed in the glass fiber layer, and the impregnation property into the glass fiber was good.

Next, a bathtub-shaped molded product was obtained in the same manner as in Example IV-1 using the SMC from which this film was peeled. Although the obtained molded product did not have underfill, it had many defects due to bubbles on the surface and had a very poor appearance.

With respect to Example IV-1 to Example IV-7 and Comparative Example IV-1 to Comparative Example IV-2, the composition of the prepared acrylic resin composition is shown in Table IV-1 below. The viscosity of the mix is shown in Table IV-2 below, and the evaluation results of the obtained molded product are shown in Table IV-3 below.

Table IV—1

The abbreviations in the table are as follows.

MM A: Methyl methacrylate

NPG: Neopentyl glycol dimethacrylate

NS # 200: Heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name "NS #

200 ")

BW33 ST: Aluminum hydroxide (Nippon Light Metal Co., Ltd. product name "BW_3

3 ST ")

Table IV—2

[Example V-1]

Methyl methacrylate (acrylic ester M) 8. 2 parts and 1,3-butylene glycol dimethacrylate (Mitsubishi Rayon Co., Ltd., trade name "Atariester BD") 16. Polymerization to 6 parts acrylic monomer 0.004 part of 2,6-di-t-butyl-4-methylphenol (manufactured by Sumitomo Chemical Co., Ltd., trade name) as an inhibitor 0.001 part of UV absorber, 1 ^ is hydrogen in the general formula (I) as an ultraviolet absorber A benzotriazole compound in which R ₂ is a t-butyl group 0.24 parts of Hindamine-based compound (trade name "Sanol LS-770" manufactured by Sankyo Co., Ltd.) 0.16 parts as light stabilizer Then, 4.4 parts of the acrylic polymer (P-5) obtained in Production Example 7 was dissolved to prepare an acrylic syrup.

To this acryl-based syrup, 0.7 parts of t-butyl peroxy _ 3,5,5-trimethylhexanoate (trade name “Trigonox 42”, manufactured by Kayaku Axo Co., Ltd.) as a curing agent, and calcium carbonate (inorganic filler) 44.8 parts, trade name “S-light # 1 200”, manufactured by Nitto Powder Chemical Co., Ltd., 0.1 part of zinc stearate as an internal mold release agent, and powdered acrylyl obtained in Production Example 8 as a thickener Six parts of the polymer (p_6) were mixed to prepare a mixture composed of an acrylic monomer, an acrylic polymer, an inorganic filler, an ultraviolet absorber, a light stabilizer, and other additives.

This mixture 8 1. Apply 2 parts to a thickness of 1 mm on two polypropylene release films, and apply a glass fiber roving of 13 m diameter as a fiber reinforcing agent to the surface of the one film where the mixture was applied. (ER4800 LBAF 210W) was cut into 25.4 mm, 20 parts were added, and the surface of the other film on which the mixture was applied was overlapped, and the glass fiber was impregnated with the mixture. Next, this impregnated material was aged at 40 ° C. for 3 days to obtain an acrylic SMC. Next, using this acrylic SMC, the upper mold temperature was set at 125 ° C, the lower mold temperature was set at 110 ° C, and the pressure was set at 8 MPa. A panel for the outer wall of mm was molded. The appearance of the obtained molded product was good. The gloss of the molded product was 80, the lightness index L * was 89.08, the chroma takeness index a * was 1.16, and b * was 4.02.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. After the test, the gloss retention was 95%, the color difference AE * _ab was 0.98, the parameter J determined by equation (2) was 0.4, and the weather resistance was good. Also, no embossing of glass fiber was observed.

[Example V-2]

'' As an ultraviolet absorber, a benzotriazole-based compound in which R i and R ₂ are both t-amyl groups in the general formula (I) (Ciba Chemical Co., Ltd. Acrylic SMC was obtained in the same manner as in Example V_1 except that 0.08 part of Nuvin 3 288 ") was used. Using this acryl-based SMC, the upper mold temperature is 130 ° C, the lower mold temperature is 110 ° C, and the pressure is 1 OMPa. O mm, 6 mm thick water tank panels were molded. The obtained molded product had good fS. The gloss of this molded product was 78, the lightness index L * was 89.41, the chroma takeness index a * was 1.84, and b * was 3.40.

A test piece was ejected from the molded article and subjected to an accelerated exposure test for 150 hours. The gloss retention after the test was 95%, the color difference AE * _ab was 0.02, the parameter J obtained by equation (2) was 1.3, and the weather resistance was very good. . Also, no embossing of glass fibers was observed.

[Example V-3]

The acrylic SMC obtained in Example V-2 was heated and cured under the conditions of an upper mold temperature of 125 ° C., a lower mold temperature of 110 ° C., and a pressure of 1 OMPa. Panels for containers of 0 mm X 180 O mm and 5 mm thickness were molded. The appearance of the obtained molded product was good. The gloss of the molded product was Ί8, the lightness index L * was 89.41, the chromaticness index a * was 1.84, and b * was 3.40.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 150 hours. The gloss retention after the test is 95 ° /. The color difference AE * _ab was 0.02, the parameter J determined by equation (2) was 1.3, and the weather resistance was very good. Also, no embossing of glass fiber was observed. .

[Example V-4]

Using the acrylic SMC obtained in Example V-2, the upper mold temperature was 130 ° C. and the lower mold temperature was 110. C. The composition was cured by heating under the conditions of a pressure of 10 MPa, and a box for a traffic light of 65 mm × 350 mm × 10 O mm was formed. The appearance of the obtained molded product was good. The gloss of this molded product was 78, the lightness index L * was 89.41, the chromatitaness index a * was 1.8.4, and b * was 3.40.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 150 hours. The gloss retention after the test was 95%, the color difference AE * _ab was 0.02, the parameter J obtained by equation (2) was 1.3, and the weather resistance was very good. . Also, glass Embossing of the fiber was not recognized.

[Example V-5]

Using the acrylic SMC obtained in Example V-2, heat curing was performed at an upper mold temperature of 125 ° C, a lower mold temperature of 110 ° C, and a pressure of 12 MPa, and a diameter of 400 mm and a height of 500 mm A box for a transformer was molded. The appearance of the obtained molded product was good. The gloss of this molded product was 78, the lightness index L * was 89.41, the chroma takeness index a * was 1.84, and b * was 3.40.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. The gloss retention after the test was 95%, the color difference AE * _ab was 0.02, the parameter J determined by equation (2) was 1.3, and the weather resistance was very good. Also, no embossing of glass fiber was observed.

[Example V-6]

The acrylic SMC obtained in Example V-2 was heated and cured under the conditions of an upper mold temperature of 140 ° C, a lower mold temperature of 125 ° C, and a pressure of 1 OMPa, and a diameter of 60 Omm and a thickness of 60 mm. A 6 mm parabolic antenna was molded. The appearance of the obtained molded product was good. The gloss of the molded product was 78, the lightness index L * was 89.41, the chroma takeness index a * was 1.84, and b * was 3.40.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. After the test, the gloss retention was 95%, the color difference AE * _ab was 0.02, the parameter J determined by equation (2) was 1.3, and the weather resistance was very good. Also, no embossing of glass fibers was observed.

[Example V-7]

Aluminum hydroxide (trade name “BW-33”, manufactured by Nippon Light Metal Co., Ltd.) is used as the inorganic filler, and benzotriazole, in which R ₂ is a t-butyl group in formula (I), is used as the ultraviolet absorber. An acrylyl-based SMC was obtained in the same manner as in Example V-1, except that 0.08 part of a system compound (trade name: “Tinuvin 320”, manufactured by Ciba-Sharity Chemicals Co., Ltd.) was used. Using this acryl-based SMC, a solar cell of 75 OmmX 60 Omm and height of 35 mm was cured by heating under the conditions of upper mold temperature of 130 ° C, lower mold temperature of 110 ° C and pressure of 1 OMPa. Panel was formed. Get The appearance of the molded article obtained was good. The gloss of the molded product was 78, the lightness index L * was 81.4.4, the chroma takeness index a * was 1.41 and b * was 3.22.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 150 hours. The gloss retention after the test was 95%, the color difference AE * _ab was 0.06, the parameter J determined by equation (2) was 3.5, and the weather resistance was very good. . Also, no embossing of glass fiber was observed.

[Example V-8]

Methyl methacrylate 5. 9 parts and neopentylglycol dimethacrylate (NK esterol NPG) 11.9 parts of an acrylic monomer and 2,6-di-t-butyl 4- as a polymerization inhibitor -Methylphenol (Sumilyzer-1 BHT) 0.004 parts, as an ultraviolet absorber, a benzotriazole compound (Tinuvin 320) in which R 1 and R ₂ are both t_butyl groups in the general formula (I) 0.0 3 Parts, 0.08 parts of a hindered amine compound (Sanol LS-770) as a light stabilizer was added, and 3.1 parts of the acrylyl polymer (p-5) obtained in Production Example (1) was dissolved. Thus, an acryl-based syrup was prepared.

To this acryl-based syrup, 0.4 parts of t-butylpropyloxy 3,4,5,5-trimethylhexanoate as a curing agent, 41.8 parts of calcium carbonate (NS # 200) as an inorganic filler, 41.8 parts, inside 0.2 part of zinc stearate as a release agent, 1 part of a green inorganic pigment as a pigment, and 5.3 parts of a powdery acryl-based polymer (p-6) obtained in Production Example 8 as a thickener Then, a mixture comprising an acrylic monomer, an acrylic polymer, an inorganic filler, an ultraviolet absorber, a light stabilizer, and other additives was prepared. Apply 69.6 parts of this mixture to a thickness of 1 mm on two polypropylene release films, and apply a glass fiber with a diameter of 13 μm as a fiber reinforcing agent to the surface of the one film where the mixture was applied. Cut the roving (ER4800 L BAF 2.10W) to 25.4 mm, add 32 parts, and place the other film on the surface coated with the mixture of the other film. Was impregnated.

Next, this impregnated material was aged at 40 ° C. for 3 days to obtain an acrylic SMC. Next, using this acryl-based SMC, the upper mold temperature was set at 130 ° C, the lower mold temperature was set at 110 ° C, and the pressure was set at 1 OMPa. 4 0 Omm, thickness An L-shaped bench with a body of 5 mm, a backrest of 40 OmmX 4 ° Omm, and a thickness of 5 mm was molded. The appearance of the obtained molded product was good. The gloss of this molded product was 81, the lightness index L * was 41.2, the chroma takeness index a * was 14.0, and b * was 12.5.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. After the test, the gloss retention was 89%, the color difference AE * _ab was 9.3, and the parameter J determined by equation (2) was 5.3, indicating that the weather resistance was extremely good. In addition, the emergence of glass fiber was not recognized.

[Example V-9]

An acrylyl SMC was obtained in the same manner as in Example V-8, except that the addition amount of the ultraviolet absorber was changed to 0.51 part and the addition amount of the light stabilizer was changed to 0.15 part. Using this acrylic SMC, it is heated and cured under the conditions of upper mold temperature of 130 ° C, lower mold temperature of 110 ° C, and pressure of 10MPa, and a manhole cover with a diameter of 60 OmmX and a thickness of 3 Omm. Was molded. The appearance of the obtained molded article was good. The gloss of this molded product was 81, the lightness index L * was 41.0, the chroma takeness index a * was 19.8, and b * was 12.4.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. The gloss retention after the test was 85%, the color difference AE * _ab was 6.5, and the parameter J determined by equation (2) was 8.2, indicating that the weather resistance was extremely good. In addition, no prominence of glass fiber was observed.

[Example V-10]

Using the acrylic SMC obtained in Example V-2, heat-curing was performed at an upper mold temperature of 125 ° C, a lower mold temperature of 110 ° C, and a pressure of 12 MPa, and a thickness of 150 mm X 50 mm, thickness A 50 mm Shinkansen cable cleat was formed. The appearance of the obtained molded product was good. This molded product had a gloss of 78, a lightness index L * of 89.41, a chromataneskiness a * of 1.84, and a b * of 3.40.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. After the test, the gloss retention was 95%, the color difference AE * _ab was 0.02, the parameter J determined by equation (2) was 1.3, and the weather resistance was very good. Also, glass Embossing of the fiber was not recognized.

[Comparative Example V-1]

An acryl-based SMC was obtained in the same manner as in Example V-1, except that no ultraviolet absorber and light stabilizer were added, and this was used to produce a panel for an outer wall in the same manner as in Example V-1. Was molded. The gloss of this molded product was 83, the lightness index L * was 89.55, the chroma takeness index a * was 1.51, and b * was 2.87.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. The gloss retention after the test was 77%. In addition, the color difference AE * _ab was 1.83, and the parameter J obtained by equation (2) was 0.5, indicating poor weather resistance. In addition, the emergence of glass fiber was also observed.

[Comparative Example V-2]

Using aluminum hydroxide (BW-33) as an inorganic filler, and without adding an ultraviolet absorber, a hindered amine compound as a light stabilizer (Tinuvin 123, a product of Ciba Chemical Co., Ltd.) A panel for an outer wall was obtained in the same manner as in Example V-1, except that only was added. The gloss of the molded product was 78, the lightness index L * was 81.58, the chroma takeness index a * was 0.99, and b * ¾2.32.

A test piece was cut out from the molded article and subjected to an accelerated exposure test at 1500 hours. The gloss retention after the test was 97%. The color difference ΔΕ * _ηΐ3 was 4.25, and the parameter J determined by equation (2) was 10.8, _indicating poor weather resistance.

[Comparative Example V-3]

An acryl-based SMC was obtained in the same manner as in Example V-8 except that no ultraviolet absorber and light stabilizer were added, and a dark green bench was obtained using this in the same manner as in Example V-8. Was. The gloss of this molded product was 81, the lightness index L * was 41.2, the chromaticness index a * was _39.1, and b * was 12.3.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. The gloss retention after the test was 80%. In addition, the color difference AE * _ab was 15.2, and the parameter J determined by equation (2) was 10.6, indicating poor weather resistance. In addition, the emergence of glass fiber was also observed. [Comparative Example V-4]

Example V was conducted using aluminum hydroxide (trade name “BW-103” manufactured by Nippon Light Metal Co., Ltd.) as an inorganic filler and adding only an ultraviolet absorber without adding a light stabilizer. An acrylic SMC was obtained in the same manner as in —8, and a dark green bench was obtained in the same manner as in Example V-8 using this. The gloss of the molded product was 80, the lightness index L * was 34.3, the chroma takeness index a * was 17.0, and b * was 13.4.

A test piece was cut out from the molded article and subjected to an accelerated exposure test for 1,500 hours. The gloss retention after the test was as low as 57%. Further, the color difference ΔE * _ab was 17.5, the parameter J obtained by the equation (2) was 11.0, and the weather resistance was poor. In addition, the emergence of glass fiber yarn was also observed.

The molding conditions and the like for Example V-1 to Example V-10 and Comparative Example V-1 to Comparative Example V-4 are shown in Table V-1 below, and the composition of the mixture and the evaluation results of the obtained molded articles were shown. The results are shown in Table V-2 below.

Table v- X ο

Table V—2

Composition Review a 5 Results

Glossiness

_{_(M)} (Ό lowly

, Y)) (D

· Γ (Y) (U

* 1) Retention χ GF

• "-Η- Π ι Overall Π

(Bubble) rate emboss

Evaluation Leakage A S 2 Lily Chinu PS ρ-Β

V-1 20 0.16 0.4

BD 16.6 4.4 44.8 0.24 6 〇 9 5 0.98 〇 ft ft

V-2 20 0.16 5 0.02 1.3

BD 16.6 4.4 44.8 008 08 〇 9 ◎ ◎ Al ± 1 Π () Chin '' ¾ υ

Example V-3 20 0.16

BD 16, 6 4.4 44.8 0.08 6 〇 9 5 0.02 1.3 〇 ◎ 碰 8 2 p-5 # 1200 thousand bin '328

V- 4 20 0.16 1.3

BD 16.6 4.4 44.8 0.08 6 〇 95 0.02 ◎ ◎

MMA 8.2 P-5 # 1200 Chinuhin 328 ρ-6

V-5 20 • 0.16 9 5 0.02 1.3

BD 16.6 4.4 44.8 0.08 6 〇 o ◎

MMA 8 2 p-5 # 1200 Chinu ^v y ^ R Ρ-

V-6 20 0.16

BD 16.6 4.4 44.8 0.08 6 〇 9 5 0.02 1.3 〇 ◎

MMA 8 2 p-5 BW-33 H 5 (N 320

V-7 20 0.16

BD 16.6 4.4 44.8 0.08 6 〇 9 5 0.06 3.5 ◎ ◎

MMA δ.9 ρ-δ NS # 200

V-8 32 0.08

NPG 11.9 3.1 41.8 0.03 5.3 〇 8 9 9.3 5.3 ◎ ◎ +

MMA 5.9 P-5 NS # 200 Chin 320 P-6

V-9 32 0.15

NPG 16.6 3.1 41.8 0.51 6 〇 8 5 6.5 8.2 o ® +

MMA 8.2 P-5 # 1200 Chinuhi'n 328 P-6

V- 10 20 0.16

MMA 8.2 Ρ-δ # 1200 P-6

V-1 20 7 1.83 -0.5 X X BD 16.6 4.4 44.8 6 〇 7

Ratio MMA 8.2 Ρ-δ BW-33 P-6

V-2 20 0.16 25 -0.8

BD 16.6 4.4 44.8 6-〇 9 7 4.〇 X Example MMA 5.9 P-5 Brain 200 P-6

V-3 32 80 15.2 -0.6 X X NPG 11.9 3.1 41.8 5.3 〇

MMA 5.9 P-5 BW-103 Chin'in 320 P-6

V-4 32

NPG 11.9 3.1 41.8 0.03 5.3 〇 5 7 17.5-1.0 XX

The abbreviations in Table V-2 are as follows.

MM A: Methyl methacrylate

BD: 1,3-butylene glycol dimethacrylate

NP G: Neopentinole glycol dimethacrylate

# 1200: Heavy calcium carbonate (trade name "S-Light # 1200" manufactured by Nitto Powder Chemical Co., Ltd.)

NS # 200: Heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name "NS # 200")

BW-33: Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., trade name "BW-33") BW-103: Hydroxium aluminum (Nippon Light Metal Co., Ltd., trade name: "BW-103J")

* 1) Hindered amine compound (manufactured by Sankyo Co., Ltd., trade name “SANONOLE LS-770”) Tinuvin PS: Benzo having a general formula (I) in which R 1 is a hydrogen atom and R 2 is a t-butyl group. Triazole-based compound (Cibas Charity Chemicals Co., Ltd., trade name: Tinuvin PSJ)

Tinuvin 328: a benzotriazole compound in which R 1 and R 2 are both t-amyl groups in the general formula (I) (trade name “Tinuvin 328”, manufactured by Ciba Chemical Co., Ltd.)

Tinuvin 320: Benzotriazole-based compound in which R 1 and R 2 are both t-butyl groups in the general formula (I) (product name “Tinuvin 320”, manufactured by Ciba Chemical Co., Ltd.)

[Comparative Example V—Consideration of 1-4]

Comparative Example V-1 is an example of a white molded article that does not use the ultraviolet absorber (U) and the light stabilizer (L). As a result, the molded article obtained turned yellow after the weather resistance test, and at the same time, the interface between the glass fiber and the resin deteriorated, the glass fiber was raised, and the weather resistance was poor.

Comparative Example V-2 is an example of a white molded article that does not use an ultraviolet absorber (U). As a result, the molded product obtained turns yellow after the weather resistance test and has poor weather resistance. Met.

Comparative Example V-3 is an example of a dark green molded article that does not use an ultraviolet absorber (U) and a light stabilizer (L). As a result, although the obtained molded article does not easily show yellowing after the weather resistance test, the interface between the glass fiber and the resin deteriorates and whitens, and the glass fiber appears, and the weather resistance is poor. Was.

Comparative Example V-4 is an example of a dark green molded article that does not use the light stabilizer (L). As a result, the obtained molded article deteriorated at the interface between the glass fiber and the resin and became whitened, the glass fiber was raised, and the weather resistance was poor.

As is clear from the above Examples and Comparative Examples, the use of a syrup containing a polymer having a functional group that reacts with an inorganic filler allows oxidation of divalent metals such as magnesium oxide and calcium hydroxide. Without using thickeners such as substances or hydroxides, or in the case of using divalent metal oxides or hydroxides, it is possible to thicken them in a very small amount. If SMC or BMC is cured by heating and pressurizing, resin molded products with unprecedented water resistance can be manufactured. In addition, by using a compound containing two or more acidic groups in one molecule and a compound containing two or more basic groups in one molecule, the use of divalent compounds such as magnesium oxide and hydroxide It is possible to thicken without using a thickening agent such as a metal oxide or hydroxide, and as a result, heat the sheet molding compound or BMC using this thickened material. By curing under pressure, it is possible to produce a resin molded product with excellent water resistance, which has never been seen before.

In addition, by setting the parameter I (T) of the resin composition to 0.01 or more, even in the case of SMC or BMC containing a fiber reinforcing agent, SMC or BMC having good fluidity during molding can be obtained. As a result, by using this SMC or BMC, and obtaining a molded product by heat and pressure curing, it is possible to produce a high-strength molded product with high productivity and good molded appearance. it can.

In addition, by expressing a specific complex viscosity in the resin composition, even when a fiber reinforcing agent is contained, it is possible to produce SMC or BMC having good fluidity during molding, and as a result, this SMC or BM By molding by heating and pressurizing with C, high productivity, high strength acrylic resin with good molded appearance Shapes can be manufactured.

In addition, by setting the parameter J of the resin molded product to 0.1 or more, even if a fiber reinforcing agent such as glass fiber is contained, it can be used for water tank panels, outer wall panels, container panels, and solar cells. Panels, car exterior panels, signal boxes, transformer boxes, parabolic antennas, radar domes, overpass shields, benches, park play equipment, pool play equipment, manhole covers, water meter covers, railway cable cleats, sash window frames It is possible to obtain resin molded products that can be used sufficiently for outdoor applications such as doors, fences, outboard motor covers, corrugated sheets, etc., and also to use UV absorbers and light stabilizers in combination with SMC or BMC. By containing it, a resin molded product that can be sufficiently used for outdoor use can be manufactured with high productivity.

Claims

The scope of the claims

1. A thickener comprising a syrup (S) containing an inorganic filler (F) and a polymer having a functional group that reacts with the inorganic filler (F).

2. The thickener according to claim 1, wherein the inorganic filler (F) contains an oxide or hydroxide of a divalent metal in an amount of 0.6 mass% or less based on the total amount of the syrup (S).

3. An inorganic filler (F) containing a divalent metal oxide or hydroxide in an amount of 0.6% by mass or less based on the total amount of the syrup (S), and a functional group that reacts with the inorganic filler (F). A sheet molding compound or a balta molding compound, comprising a syrup (S) containing a polymer having

4. The sheet molding compound or the balta molding compound according to claim 3, further comprising a fiber reinforcing material (Y) and a wood or stone patterning agent (W). .

5. The sheet molding compound or bar / remo / reading core according to claim 3, wherein the weight average molecular weight of the polymer in the syrup (S) is 5,000 or more.

6. The sheet molding compound or the balta molding compound according to claim 3, wherein the functional group in the syrup (S) that reacts with the inorganic filler (F) is a carboxyl group. .

7. The sheet molding compound or bulk molding compound according to claim 3, wherein the syrup (S) is an acrylic syrup.

8. It contains an inorganic filler (F) and a polymer having a functional group that reacts with the inorganic filler (F), and the content of divalent metal oxide or hydroxide is 0.6 mass. A method for producing a sheet molding compound or a bulk molding compound, wherein a syrup (S) having a mass ratio of / ₀ or less is stirred and mixed, and then aged to increase the viscosity.

9. It contains an inorganic filler (F) and a polymer having a functional group that reacts with the inorganic filler (F), and has a divalent metal oxide or hydroxide content of 0.6. Less than mass%

A resin molded product obtained by curing (S).

0. The sheet molding compound or bulk according to claim 3 A method for producing a resin molded product, comprising heating and curing a molding compound.

11.1 A thickening composition comprising a compound (A) containing two or more acidic groups in one molecule and a compound (B) containing two or more basic groups in one molecule. .

12.2 At least one of the compound (A) containing two or more acidic groups in one molecule and the compound (B) containing two or more basic groups in one molecule has a molecular weight of 100 or more. 12. The thickening composition according to claim 11, which is a compound having the following formula:

13. The thickening composition according to claim 12, wherein the compound having a molecular weight of 13.100 or more is an acryl polymer.

14. The thickening composition according to claim 11, wherein the acidic group is a propyloxyl group.

15. The thickening composition according to claim 11, wherein the basic group is an amino group.

16. The thickening composition according to claim 11, further comprising a compound (C) having neither an acidic group nor a basic group.

17.1 A compound containing two or more acidic groups in one molecule (A), a compound containing two or more basic groups in one molecule (B), and an inorganic filler (F) Seat molding compound or Balta molding compound.

18. The sheet molding compound or the balta molding compound according to claim 17, further comprising a fiber reinforcing material (Y).

19.1 At least one of the compound (A) containing two or more acidic groups in one molecule and the compound (B) containing two or more basic groups in one molecule has a molecular weight of 1000 or more. The sheet molding compound or the bulk molding compound according to claim 17, which is a compound having the following formula: .

The sheet molding compound or the balta molding compound according to claim 19, wherein the compound having a molecular weight of not less than 20.1000 is an acryl-based polymer.

21. The sheet molding compound or the vanolem molding compound according to claim 17, wherein the acidic group is a carboxyl group.

22. The sheet molding compound or the balta molding compound according to claim 17, wherein the basic group is an amino group.

23. The sheet molding compound or the bulk molding compound according to claim 17, further comprising a compound (C) having neither an acidic group nor a basic group.

24. Compound (A) containing two or more acidic groups in one molecule and compound (B) containing two or more basic groups in one molecule, and then aging to increase the viscosity A method for producing a thickening composition, characterized by comprising:

25. After mixing compound (A) containing two or more acidic groups in one molecule, compound (B) containing two or more basic groups in one molecule, and inorganic filler (F) A method for producing a bulk molding compound, characterized by aging and thickening. .

26. A compound (A) containing two or more acidic groups in one molecule, a compound (B) containing two or more basic groups in one molecule, and an inorganic filler (F) are mixed, A method for producing a sheet molding compound, comprising impregnating the mixture with a fiber reinforcing material (Y), and then aging and thickening the mixture.

27. A method for producing a resin molded article, comprising curing the viscous composition according to claim 11 under heat and pressure.

28. A method for producing a resin molded product, comprising heating and curing the sheet molding compound or the balta molding compound according to claim 17.

29. A luster composition comprising a monomer (m), a polymer (p) and an inorganic filler (F), a composition (X), a fiber reinforcing agent (Y), and a curing agent (Z). In the sheet molding compound or bulk molding compound, the parameter I (T) represented by the following formula (1) must be 0.01 or more at any temperature T within the range of 20 to 80 ° C. Feature sheet molding compound or bulk molding compound.

I (T) = t a η δ (Τ) one 0.0021T— 0.0962 (l)

(Where tan S (T) is the loss tangent of the resin composition (X) at the temperature Τ, Temperature T is degrees Celsius. )

30. A resin composition comprising a resin composition (X) comprising a monomer (m), a polymer (p) and an inorganic filler (F), a fiber reinforcing agent (Y), and a curing agent (Z). In the molding compound or the parc molding compound, the complex viscosity of the resin composition (X) is

(I) a complex viscosity at 3 0 ^{l X 1 0 3 P a ·} s~l X 1 0 7 in the range of P a · s, and (ii) 80 ° complex viscosity is 30 ° C at C Less than 0.2 times

A sheet molding compound or a bulk molding compound.

31. The sheet molding compound or the balta molding compound according to claim 29 or 30, wherein the resin composition (X) is an acrylic resin composition.

32. The sheet molding compound or the bulk molding compound according to claim 29 or 30, further comprising a resin composition (X) and a stone pattern material (W).

33. The sheet / reading compound or bulk molding compound according to claim 32, wherein the stone pattern material (W) is an inorganic filler-containing resin particle.

34. Resin composition (X) 20-99% by mass, Fiber reinforcing agent (Y):! -80% by mass, and curing agent (Z) 0.01-10% by mass in the total amount of sheet molding compound or Balta molding compound 31. The sheet mono reading compound or the vanolec mono reading compound according to claim 29 or 30, comprising:

35. An ataryl resin molded product obtained by heating and curing the sheet molding compound or the balta molding compound according to claim 29 or 30.

36. Sheet molding compound containing monomer (m), polymer (p), inorganic filler (F), fiber reinforcing agent (Y), ultraviolet absorber (U) and light stabilizer (L) or Banoreck molding compound. '37. The sheet molding compound or the balta molding compound according to claim 36, wherein at least one of the monomer (m) and the polymer (p) is an acrylic monomer or polymer.

38. The seat molding compound or the back molding compound according to claim 36, wherein the ultraviolet absorbent (U) contains at least a compound (U1) having a maximum absorption wavelength in a wavelength range of 280 to 380 nm.

39. Compounds having a maximum absorption wavelength in the wavelength range of 280 to 380 nm (U1) Force Benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, salicylates 1, and compounds 39. The sheet molding compound or the balta molding compound according to claim 38, which is at least one compound selected from the group consisting of:

40. The compound (U1) having a maximum absorption wavelength in the wavelength range of 280 to 380 nm (U1) A benzotriazole compound represented by the following general formula (I): The sheet molding compound or the balta molding compound according to claim 36.ゥ

(In the formula, R ₁ R ₂ represents a hydrogen atom or an alkyl group.)

41. The sheet molding compound or the balta molding compound according to claim 36, which is a light stabilizer (L) a hindered amine compound.

42. Seat molding accommodation. Monomer (m) 5 to 95% by mass, Polymer (p) 0.1 to 40% by mass, and Inorganic filler (F) 5 to 95% by mass in the total amount of the compound or Baltamolding compound. /. , Fiber reinforcement (Y) :! 37. The sheet molding comparator according to claim 36, comprising about 50% by mass, an ultraviolet absorbent (U) 0.001 to: 1% by mass, and 0.001 to 1% by mass of a light stabilizer (L). Command or bulk mall n

43. A resin molded product containing an inorganic filler (F) and a fiber reinforcing agent (Y). The conditions are as follows: Sunshine ゥヱ Zometer, black panel temperature 63 ° C, rainfall of 12 minutes out of 60 minutes. After the accelerated exposure test for 1,500 hours under the following conditions, the molded article after the test has a gloss retention of 70% or more and the parameter J represented by the following formula (2) is 0.1 or more. Molded resin products.

J = 26-0. 276 L * -AE * _ab … (2)

(In the formula, L * is the lightness index of the molded article before the test, and ΔE * _ab is the color difference between the molded article before and after the test.)

44. The resin molded product according to claim 43, which is an acryl-based resin molded product.

45. Sheet molding compound containing monomer (m), polymer (p), inorganic filler (F), fiber reinforcing agent (Y), ultraviolet absorber (U) and light stabilizer (L) or 44. The resin molded product according to claim 43, wherein the bulk molding compound is cured by heating and pressing.