JP5915251B2 - Curable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable resin composition excellent in surface appearance and antifouling property and a cured molded product thereof.

  Artificial marble is generally a cured resin composition composed of resin, inorganic filler, low shrinkage agent, catalyst, cross-linking agent, pigment, etc., and it is relatively inexpensive, while its workability, workability, strength, etc. It is a resin molded product that is excellent in appearance and close in appearance to natural marble. For this reason, it has been widely used as an antifouling material suitable for bathtubs, washing places, countertops, kitchen top plates, sanitary applications, and the like. However, since the application is mainly used for water, adhesion of various types of dirt such as scale becomes a big problem, and many studies have been made to solve these problems.

  For example, Patent Document 1 discloses a resin molded product obtained by curing a resin composition containing a curable resin, an inorganic filler, and an organic fluorine compound. The organic fluorine compound used there is a fluorine homopolymer, a fluorine random copolymer, a fluorine oil or a low molecular fluorine surfactant. Patent Document 2 discloses a resin molded product obtained by curing a resin composition containing an aggregate, a low-molecular fluorine-based compound, and a curable resin.

JP 11-343350 A Japanese Patent Laid-Open No. 10-168198

  However, in the resin molded products disclosed in Patent Document 1 and Patent Document 2, since compatibility between the organic fluorine compound or the low molecular fluorine compound and the curable resin is very poor, it is difficult to mix the two uniformly. In addition, even after molding, the organic fluorine compound and the low molecular fluorine compound are easily released on the surface. Therefore, since the organic fluorine compound and low molecular fluorine compound on the surface easily fall off, it has been difficult to maintain the desired water and oil repellency.

  Furthermore, when a fluorine-based random copolymer is used as the organic fluorine compound, the compatibility with the synthetic resin decreases if the amount of fluorine is large, so that the same phenomenon as described above occurs, and the water and oil repellency is maintained. It is difficult. Further, if the amount of fluorine is lowered in order to increase the compatibility with the synthetic resin, the orientation of the fluorine-based random copolymer on the surface becomes poor and it becomes difficult to ensure the desired water and oil repellency.

  The present invention has been made in view of the above problems, and an object of the present invention is to ensure water and oil repellency, and to provide a curable resin composition excellent in surface appearance and antifouling property and cured molding thereof. Is to provide things.

（一般式（Ｉ）において、Ｒ１は、水素原子、メチル基、フッ素原子又は塩素原子であり、Ｒ２は、炭素数１以上の脂肪族基である。）
第２の発明は、含フッ素セグメントと非フッ素セグメントからなるフッ素系ブロック共重合体と、硬化性樹脂と、を含む硬化性樹脂組成物であって、前記含フッ素セグメントを構成する含フッ素単量体が、炭素数６のパーフルオロアルキル基を有する上記一般式（Ｉ）に示される含フッ素単量体であり、
前記非フッ素セグメントは、メタクリル酸メチル４０〜４１．１重量％、メタクリル酸ブチル４０〜４１．１重量％、メタクリル酸２−ヒドロキシエチル１６．７重量％、及びメタクリル酸１．１〜３．３重量％の合計１００重量％からなる共重合体であり、
低収縮剤を含まないことを特徴とする硬化性樹脂組成物である。
第３の発明は、含フッ素セグメントと非フッ素セグメントからなるフッ素系ブロック共重合体の前記含フッ素セグメントが５〜９５重量％であることを特徴とする第１又は第２の発明に記載の硬化性樹脂組成物である。
第４の発明は、前記硬化性樹脂１００重量部に対して、前記フッ素系ブロック共重合体０．０１〜５０重量部を含有することを特徴とする第１から第３の発明のうちいずれかの硬化性樹脂組成物である。
第５の発明は、第１から第４の発明のうちのいずれかの硬化性樹脂組成物を硬化させて得られることを特徴とする硬化性樹脂の硬化成形物である。
第６の発明は、硬化時に加熱成形して得られることを特徴とする第５の発明の硬化性樹脂の硬化成形物である。 That is, the first invention is a curable resin composition comprising a fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment, a curable resin, and a low shrinkage agent, wherein the fluorine-containing segment Is a fluorine-containing monomer represented by the following general formula (I) having a C6 perfluoroalkyl group,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
The low shrinkage agent is a polystyrene-based resin, and is contained in an amount of 1 to 150 parts by weight with respect to 100 parts by weight of the curable resin.

(In the general formula (I), R1 is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and R2 is an aliphatic group having 1 or more carbon atoms.)
The second invention is a curable resin composition comprising a fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment, and a curable resin, wherein the fluorine-containing single monomer constituting the fluorine-containing segment Is a fluorine-containing monomer represented by the above general formula (I) having a perfluoroalkyl group having 6 carbon atoms,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
It is a curable resin composition characterized by not containing a low shrinkage agent.
The third invention is the curing according to the first or second invention, characterized in that the fluorine-containing segment of the fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment is 5 to 95% by weight. It is an adhesive resin composition.
4th invention contains 0.01-50 weight part of said fluorine-type block copolymers with respect to 100 weight part of said curable resin, Any one of 1st-3rd invention characterized by the above-mentioned. The curable resin composition.
A fifth invention is a curable resin cured product obtained by curing the curable resin composition of any of the first to fourth inventions.
A sixth invention is a cured molded product of the curable resin according to the fifth invention, which is obtained by heat molding at the time of curing.

  ADVANTAGE OF THE INVENTION According to this invention, while ensuring water and oil repellency, the curable resin molding excellent in surface appearance and antifouling property, and its cured molding can be provided.

  Hereinafter, embodiments of the present invention will be described in more detail. The curable resin composition of the present invention (hereinafter sometimes simply referred to as a resin composition) is a resin composition containing a fluorine-based block copolymer and a curable resin. The cured molded product is obtained by curing a resin composition. As the form, in addition to what is formed by itself, the form which covers the surface of an article | item, the thing which impregnated the base material and hardened | cured are included.

[Fluoro-based block copolymer]
The fluorine-based block copolymer is a block copolymer (block polymer) composed of a fluorine-containing segment and a non-fluorine segment.

  The fluorine-containing segment is composed of either a homopolymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer. The fluorine-containing monomer constituting the fluorine-containing segment has a C6 perfluoro group and is represented by the following general formula (I).

In the general formula (I), R ₁ is a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

In the general formula (I), R ₂ is an aliphatic group having 1 or more carbon atoms. An alkylene group having 1 to 50 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms and 18 to 24 carbon atoms is more preferable.

  Further, as a fluorine-containing segment, a non-fluorine monomer used for forming a copolymer of a fluorine-containing monomer and a non-fluorine monomer can be radically polymerized without containing a known fluorine. All of the monomers are included. In the case of a fluorinated segment composed of a copolymer of a fluorinated monomer and a non-fluorinated monomer, the proportion of the polymerized portion based on the fluorinated monomer in the fluorinated segment is 80% by weight or more. It is preferably 85% by weight or more, more preferably 95% by weight or more. If it is less than 80% by weight, it tends to be difficult to develop sufficient water and oil repellency.

  The non-fluorine segment is formed mainly of a non-fluorine monomer alone or a non-fluorine monomer. Non-fluorinated monomers used for forming the non-fluorine segment include all known radically polymerizable monomers not containing fluorine. Moreover, the same thing as the non-fluorine-type monomer used in order to form the copolymer of the fluorine-containing monomer comprised as a fluorine-containing segment and a non-fluorine-type monomer can be used.

  Among these, as a monomer that provides a sufficient polymerization conversion rate, ensures compatibility with the curable resin component, and does not impair the water repellency of the cured molded product, the following general formula (A) And other non-fluorinated monomers. These are used alone or in combination of two or more.

  R3 in the general formula (A) is a hydrogen atom or a methyl group. R4 represents an alkyl group or substituted alkyl group having 1 to 22 carbon atoms, a cycloalkyl group or substituted cycloalkyl group having 3 to 15 carbon atoms, a phenyl group or a substituted phenyl group.

  Specific examples of the general formula (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid hexadecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic Glycidyl acid, benzyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid amide N, N-dimethyl, N-methylol (meth) acrylamide, N- (meth) acryloylmorpholine, (meth) acrylic acid, ( (Meth) acrylonitrile, vinyl acetate, styrene, methoxystyrene, - methyl maleimide, N- ethylmaleimide, N- phenylmaleimide, diisopropyl fumarate, di-t- butyl, dicyclohexyl fumarate, dibenzyl fumarate, be mentioned as dimethyl itaconate and the like are preferable.

  The proportion of the fluorine-containing segment in the fluorine-based block copolymer is 5 to 95% by weight, preferably 10 to 70% by weight, and more preferably 20 to 50% by weight. When the fluorine-containing segment is less than 5% by weight, the performance as the fluorine-containing segment, that is, water / oil repellency cannot be sufficiently obtained. If it exceeds 95% by weight, it tends to be difficult to ensure compatibility with the curable resin component.

  Regarding the molecular weight of the fluorine-based block copolymer, the number average molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 300,000, and more preferably 10,000 to 100,000. If it is less than 5,000, the performance of fluorine, that is, water / oil repellency, is not sufficiently exhibited, and if it exceeds 1,000,000, it tends to be difficult to produce.

  Next, the manufacturing method of a fluorine-type block copolymer is demonstrated. The fluorine-based block copolymer is, for example, a fluorine-containing monomer constituting a fluorine-containing segment or a fluorine-containing monomer and a non-fluorine by a bulk polymerization method, a suspension polymerization method, a solution polymerization method or an emulsion polymerization method. It can be synthesized by mixing a monomer and a non-fluorine monomer constituting a non-fluorine segment, and adding a polymerization initiator. As the polymerization initiator, an organic peroxide, an inorganic peroxide, an azo compound, or the like can be used. Among these, the use of polymeric peroxide is preferable in that a block copolymer can be efficiently obtained by controlling the cleavage of the peroxide bond in the peroxide bond-containing copolymer without using a catalyst or the like. For example, this fluorine-based block copolymer can be produced by a known production process using, for example, polymeric peroxide as a polymerization initiator (for example, Japanese Patent Publication Nos. 5-41668 and 5-59942).

  The polymeric peroxide used in the production of the above-mentioned fluorine-based block copolymer is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, one or more of various polymer peroxides described in JP-B-5-59942 can be used. Those represented by the following formulas (1), (2) and (3) can be used as preferred examples.

  (In the formula, n is an integer of 1 to 10, and m is a polymeric peroxide represented by an integer of 2 to 20.)

  (In the formula, n is a polymeric peroxide represented by an integer of 2 to 20.)

  (Wherein n is a diacyl polymeric peroxide represented by an integer of 3 to 20)

  The fluorine-based block copolymer can be easily obtained by the usual bulk polymerization method, suspension polymerization method, solution polymerization method and emulsion polymerization method using the above-mentioned polymeric peroxide. For example, in the case of a solution polymerization method, as a first step, first, a polymer peroxide is used as a polymerization initiator, and the non-fluorine monomer that forms a non-fluorine segment is polymerized in a solution, whereby a peroxide is introduced into the chain. A peroxide bond-containing non-fluorinated polymer into which bonds are introduced is obtained.

  Next, in the second step, when the polymerization is carried out by adding a fluorine monomer to the solution obtained in the first step, the peroxide bond in the peroxide bond-containing non-fluorine polymer is cleaved, and the efficiency A block copolymer can be obtained well. In the two-stage polymerization as described above, the non-fluorine monomer in the first step may be used in the second step, and the fluorine monomer in the second step may be used in the first step.

[Curable resin]
The curable resin includes all known curable resins, and includes, for example, all known resins used for artificial marble, paints, and gel coating agents. Specific examples of the curable resin used include resins such as unsaturated polyester resins, vinyl ester resins, and curable (meth) acrylic resins. The curable resin may be used alone or in combination of two or more.

  The unsaturated polyester resin is obtained by dissolving an unsaturated polyester obtained by heating and dehydrating condensation of an unsaturated dibasic acid, a saturated dibasic acid, and a polyhydric alcohol at a specific ratio in a radical polymerizable monomer. Any known resin can be used.

  Examples of the unsaturated dibasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid and the like, and are selected from one or more of these. Examples of the saturated dibasic acid include aromatic dibasic acids such as phthalic anhydride, orthophthalic acid, isophthalic acid, and terephthalic acid, and aliphatic dibasic acids such as adipic acid, succinic acid, and sebacic acid. Selected from one or more of the following.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, and hydrogenated bisphenol A. An ethylene oxide or a propylene oxide adduct is mentioned, It selects from 1 type, or 2 or more types of these groups.

  Examples of the radical polymerizable monomer include the monomer of the general formula (A), other non-fluorine monomers, fluorine monomers, and the like, and are selected from one or more of these groups. The The blending ratio of the unsaturated polyester in the unsaturated polyester resin is preferably 30 to 80% by weight. If it is less than 30% by weight, the mechanical properties of the cured product tend to deteriorate. Moreover, when it exceeds 80 weight%, the viscosity of unsaturated polyester resin will become high, and it exists in the tendency for workability | operativity to fall.

  The vinyl ester resin is an epoxy group of an epoxy resin having two or more epoxy groups in one molecule and an unsaturated monobasic acid such as acrylic acid or methacrylic acid or an unsaturated dibasic acid such as maleic acid or fumaric acid. It is a liquid resin in which a reaction product obtained by ring-opening addition of a monoester is dissolved in a radical polymerizable monomer, and any known resin can be used.

  Specific examples of the epoxy resin include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin or bisphenol S type epoxy resin synthesized from bisphenol A, bisphenol F or bisphenol S and epichlorohydrin; phenol A phenol novolac-type epoxy resin synthesized from a so-called phenol novolak resin and epichlorohydrin obtained by reacting aldehyde with formaldehyde in the presence of an acidic catalyst; and a so-called cresol novolak resin obtained by reacting cresol and formaldehyde in the presence of an acidic catalyst Examples thereof include novolak-type epoxy resins such as cresol novolak-type epoxy resins synthesized from epichlorohydrin.

  As the radical polymerizable monomer, any of the monomers in the unsaturated polyester resin can be used, and the monomer is selected from one or more of these groups. The blending ratio of the unsaturated epoxy resin in the vinyl ester resin is preferably 30 to 90% by weight. If it is less than 30% by weight, the corrosion resistance and heat resistance of the cured vinyl ester resin obtained therefrom tend to deteriorate. On the other hand, when it exceeds 90% by weight, the viscosity of the vinyl ester resin obtained from this increases, and the workability tends to deteriorate.

The curable (meth) acrylic resin is usually a (meth) acrylic resin and a radical polymerizable monomer having two or more unsaturated groups in one molecule (hereinafter abbreviated as a crosslinking agent) as a solvent. It refers to (meth) acrylic syrup dissolved in a radical polymerizable monomer, and any known one can be used.
The (meth) acrylic resin is obtained by polymerizing (meth) acrylic acid ester with an organic peroxide or an azo compound. As the (meth) acrylic acid ester, any known (meth) acrylic acid ester can be used. Specific examples include the monomer represented by the general formula (A). These (meth) acrylic acid esters are usually used by selecting one or two or more kinds, and it is particularly preferable to contain 50% by weight or more of methyl methacrylate. By containing 50% by weight or more of methyl methacrylate, a cured molded article having excellent weather resistance, transparency, and surface gloss can be obtained.

  Further, as other components of the (meth) acrylic resin, for example, unsaturated monobasic acids such as (meth) acrylic acid and crotonic acid, unsaturated dibasic acids such as maleic acid, fumaric acid and itaconic acid, these unsaturated A monoester of dibasic acid, styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, t-butyl styrene, chlorostyrene, and vinyl esters such as vinyl acetate and vinyl propionate are included in an amount of 30% by weight or less. You can also.

  As the radical polymerizable monomer as the solvent, any of the monomers in the unsaturated polyester resin can be used, and it is selected from one or more of these groups.

  Specific examples of the crosslinking agent include, for example, ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as neopentyl glycol di (meth) acrylate, and diethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, allyl (meth) acrylate, diallyl phthalate, vinyl (meth) acrylate, vinyl crotonate, etc., one or two of these groups The above is selected.

  The content of the crosslinking agent in the total amount of the radical polymerizable monomer and the crosslinking agent as a solvent is preferably 1 to 20% by weight, more preferably 3 to 15% by weight. When the content of the crosslinking agent is less than 1% by weight, the heat resistance of a cured molded product obtained therefrom tends to deteriorate. On the other hand, when the content of the crosslinking agent exceeds 20% by weight, the cured molded product obtained therefrom tends to be brittle.

  The blending ratio of the (meth) acrylic resin in the curable (meth) acrylic resin is preferably 10 to 50% by weight. When the (meth) acrylic resin is less than 10% by weight, the cured product obtained from this tends to crack. When the (meth) acrylic resin exceeds 50% by weight, the viscosity of the thermosetting (meth) acrylic resin increases, and the workability tends to deteriorate.

  In the resin composition of the present invention, one type or two or more types of fluorine-based block copolymers can be mixed and used. However, the amount of the fluorine-based block copolymer used is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the curable resin. If it is less than 0.01 part by weight, it is difficult to develop water and oil repellency, and if it exceeds 50 parts by weight, the strength of the resin molded product tends to be impaired. More preferably, it is 0.1-10 weight part, More preferably, it is 0.1-5 weight part.

  The amount of the curable resin used is preferably 10 to 85% by weight in the resin composition, more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight. If it is less than 10% by weight, the strength of the cured molded product tends to be impaired, and if it exceeds 60% by weight, shrinkage during molding tends to be large, and molding itself tends to be difficult.

  Various additives can also be added to the resin composition within a range that does not impair the effects of the present invention, depending on the application.

  For example, a low shrinkage agent can be added. The low shrinkage agent is an additive for suppressing molding shrinkage when thermosetting the thermosetting resin composition. Examples of the low shrinkage agent include polystyrene low shrinkage agents and acrylic low shrinkage agents. Among them, the polystyrene-based low shrinkage agent tends to orient the fluorine-containing segment of the fluorine-based block copolymer on the surface of the cured molded product. Therefore, a polystyrene-based low shrinkage agent is preferable in that water and oil repellency is easily exhibited. Examples of the polystyrene-based low shrinkage agent include polystyrene, a block copolymer containing 10 to 99.9 parts by weight of polystyrene as a segment, crosslinked polystyrene, and a mixture thereof. Any of these low shrinkage agents may have a reactive group. Moreover, the mixture which contains 0.1-50 weight% of polystyrene separation inhibitors in the said polystyrene-type low shrinkage agent is also contained. The above-mentioned polystyrene separation inhibitor is an agent that suppresses aggregation of polystyrene and uniformly disperses polystyrene in the curable resin composition, and is a block copolymer or graft copolymer having excellent compatibility between the curable resin and polystyrene. A polymer etc. are mentioned. Moreover, the compounding ratio of the low shrinkage agent is preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the curable resin. If it is 1 part by weight or less, it is difficult to suppress molding shrinkage, and if it exceeds 150 parts by weight, the strength of the molded product tends to be impaired.

  In addition, a filler can be added to improve physical properties such as mechanical strength, thermal conductivity, and heat resistance of the molded product. As the filler, all known inorganic or organic fillers can be used and are not particularly limited. For example, aluminum hydroxide, aluminum silicate, glass frit, silica, calcium hydroxide, calcium silicate, calcium carbonate, calcium sulfite, calcium sulfate, magnesium hydroxide, barium sulfate, titanium oxide, antimony trioxide, powder talc, powder Quartz, calcite, diatomaceous earth, clay minerals, powdered chalk, marble, limestone, borax and the like can be mentioned as preferred fillers. In addition, a filler may be individual and may be used in mixture of 2 or more types. The particle size is preferably 1 to 200 μm, more preferably 5 to 150 μm, and still more preferably 10 to 80 μm. If it is less than 1 μm, the hot water resistance tends to decrease, and if it exceeds 200 μm, the surface smoothness of the cured molded product tends to be impaired.

  The amount of the inorganic filler used is preferably 35 to 85% by weight in the resin composition, more preferably 50 to 80% by weight, and still more preferably 55 to 75% by weight. If it is less than 35% by weight, the shrinkage at the time of molding increases, so that molding itself becomes difficult. If it exceeds 85% by weight, the strength of the resin molded product tends to be impaired.

  In addition, for example, antibacterial agents, dyes, pigments, ultraviolet absorbers, crosslinking agents, antioxidants, thickeners, internal mold release agents, glass fibers, resin fibers, and the like can be added.

  The resin composition containing each of the above components can be cured using a curing agent to obtain a cured molded product. Examples of the curing agent in this case include various known organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.

  The curing conditions vary depending on the organic peroxide used, but are usually 70 to 180 ° C. and 0.5 to 60 minutes. Catalysts for decomposing peroxide compounds, for example, tertiary amines such as N, N-dibutylaniline and tributylamine, acetoacetates such as ethyl acetoacetate and propylacetoacetate, cobalt naphthenate and octylic acid When a cobalt salt such as cobalt is used, it can be sufficiently cured even near room temperature. Specifically, it can be cured under conditions of 0 to 80 ° C. The amount of the catalyst used is suitably 0.005 to 0.2% by weight based on the total amount of the resin composition.

  The specific method of curing is not particularly limited as long as the desired cured molded product can be obtained. For example, hand lay-up molding method at room temperature, spray-up molding method, SMC / BMC press method, room temperature or Molding method for manufacturing FRP products such as resin transfer molding at higher temperatures, continuous molding of corrugated plates and flat plates at temperatures above room temperature, casting at room temperature or above, gel coating, lining And a flow coating method for producing a decorative board.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  First, the fluorine-type block copolymer dispersion liquid of each manufacture example shown by Table 1 was obtained. In Production Example 1, first, 600 g of methyl ethyl ketone was charged into a 5-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, heated to 70 ° C. while blowing nitrogen gas, and methyl methacrylate < MMA> 200 g, butyl methacrylate <BMA> 200 g, 2-hydroxyethyl methacrylate <HEMA> 83 g and methacrylic acid <MAA> 17 g mixed liquid and methylethylketone 400 g and polymeric peroxide 110 g simultaneously. The mixture was charged over 2 hours, and the polymerization reaction was further carried out for 4 hours. Thereby, the dispersion liquid of the polymer of MMA, BMA, HEMA, and MAA which comprises a non-fluorine segment was obtained. The composition ratio (MMA / BMA / HEMA / MAA) of each monomer in the obtained non-fluorine segment is as shown in Table 1.

Subsequently, 850 g of methyl ethyl ketone, 317 g of fluorine monomer CH ₂ ═CHCOO (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ <FA (C ₆ )>, and 17 g of methyl methacrylate <MMA> are taken over 40 minutes. The mixture was charged and subjected to a polymerization reaction for 1.5 hours, and further a polymerization reaction was performed at 80 ° C. for 3 hours to obtain a dispersion containing a fluorine-based block copolymer (Mw = 44000). The composition ratio of the non-fluorine segment and the fluorine-containing segment in the obtained fluorine-based block copolymer is 60:40 as shown in Table 1, and FA (C ₆ ) and NMA in the fluorine-containing segment are The ratio (FA (C ₆ ) / MMA) is 38/2 as shown in the table.

  Similarly, with respect to Production Examples 1-2 to 1-6 and 2-1 to 2-3, dispersions containing a fluorine-based block copolymer having the composition shown in Table 1 were obtained. The fluorine-containing monomer used in each production example is represented by the following general formula (II), and R1, R2, and Rf are as shown in Table 1.

Next, using the obtained dispersion containing the fluorine-based block copolymer according to Production Examples 1-1 to 1-6 and 2-1 to 2-3, the following curable resin, the following low shrinkage agent, and the like Thus, each cured molded product of Examples and Comparative Examples having the compositions shown in Table 2 was obtained. In addition, the compounding quantity of the fluorine-type block copolymer shown in Table 2 and a low shrinkage agent is shown by the weight ratio with respect to 100 weight part of curable resin.
In addition, the compounding quantity of a fluorine-type block copolymer is not the compounding quantity of a dispersion liquid but the compounding quantity as a fluorine-type block copolymer.

[Curable resin]
UP (1) unsaturated polyester resin (manufactured by Japan Composite Co., Ltd., Polyhope (registered trademark) R100AP)
UP (2) unsaturated polyester resin (manufactured by Japan Composite Co., Ltd., Polyhope (registered trademark) 6619)
Acrylic Acrylic resin (Nippon Iupika Co., Ltd., Neopol (registered trademark) 8101)

[Low shrinkage agent]
PS system (A) PVAc-b-PS = 10/90 (block copolymer consisting of 10 parts by weight of polyvinyl acetate and 90 parts by weight of polystyrene) (manufactured by NOF Corporation, Modiper (registered trademark) SV10B) -30)
PS system (B) Mixture of 95 parts by weight of polystyrene and 5 parts by weight of polystyrene separation inhibitor (by BYK) PS system (C) Mixture of 70 parts by weight of polystyrene and 30 parts by weight of low shrinkage agent PS system (D) PVAc-b- PS = 50/50 (a block copolymer comprising 50 parts by weight of a polyvinyl acetate segment and 50 parts by weight of a polystyrene segment) (manufactured by NOF Corporation, MODIPER (registered trademark) SV501)
PS (E) Reactive group-containing crosslinked polystyrene PVAc Polyvinyl acetate

[Examples 1-1 to 1-3, 2-1 and Comparative Examples 1-1 to 1-3]
In Examples 1-1 and 2-1, Comparative Example 1-1, the fluorine-based block copolymer and the low shrinkage agent are blended at a blending ratio shown in Table 2 with respect to 100 parts by weight of the curable resin. Add 2.0 parts by weight of methyl ethyl ketone peroxide (trade name: Permec N, manufactured by NOF Corporation) as a curing agent, and add 0.5 double parts of cobalt naphthenate as a curing accelerator, and mix for 15 minutes with a stirrer to form a liquid A curable resin composition was obtained. Then, the prepared resin composition was impregnated with a chopped strand mat of # 450 on a glass plate on which a PET film was attached, and left in a thermostatic bath at 25 ° C. for 30 minutes to obtain a cured molded product.

[Examples 2-2 to 2-21, Comparative Examples 2-1 to 2-8]
In Examples 2-2 to 2-21 and Comparative Examples 2-1 to 2-8, with respect to 100 parts by weight of the curable resin, the fluorine-based block copolymer and the low shrinkage agent are mixed at the compounding ratio shown in Table 2. While blended, 200 parts by weight of calcium carbonate powder (manufactured by Nitto Flour Chemical Co., Ltd., trade name: NS-100) as a filler, and t-butylperoxyisopropyl carbonate (manufactured by NOF Corporation, trade name: as a curing agent) Perbutyl I-75) 2.0 parts by weight, 0.05 parts by weight of parabenzoquinone as a polymerization inhibitor, 5.0 parts by weight of zinc stearate as an internal mold release agent, and 2.0 parts by weight of magnesium oxide as a thickener The mixture was mixed for 15 minutes with a stirrer to obtain a paste. Thereafter, the paste was transferred to a kneader, glass fiber (6 mm chopped strand mat; manufactured by Nippon Glass Fiber Co., Ltd., trade name: EM450G-1) was added so as to be 10% by weight, and kneaded with a kneader for 5 minutes. Thus, a curable resin composition was obtained. The obtained curable resin composition was sandwiched with a polyethylene film in a sheet shape and pressed and integrated with a roll. This integrated product was allowed to stand in an atmosphere of 40 ° C. for 24 hours to produce SMC (complex of FRP preparation process). The obtained SMC was compression-molded for 4 minutes at a molding temperature of 10 MPa using a mold temperature of 145 ° C./130° C. (lower mold / upper mold) using a 100 ton press, and a flat cured product of 150 mm × 100 mm × 4 mm Got.

  About each obtained hardening molded object, the external appearance and antifouling last name were evaluated by the following method. Moreover, the contact angle of water and the contact angle of n-dodecane were measured by a droplet method as an index of water and oil repellency. The results are also shown in Table 2.

[Appearance evaluation method]
Judging by visual inspection, the surface is glossy and glossy, and the smoothness is excellent. The case where it is is set as x.

[Evaluation of antifouling properties]
Droplet of oleic acid is placed on the surface of the sample and the removability of the droplet is judged visually when it is flowed in the shower. Good removability of the droplet (flowing with a small amount of shower) ○, poor removability of the droplet (The droplet spreads) was set as x.

Since the perfluoroalkyl group having 7 or more carbon atoms in the fluorine-containing monomer represented by the general formula (I) has crystallinity, it is crystallized when the fluorine-based block copolymer is oriented on the surface. Therefore, the surface becomes in a state like microphase separation and the surface appearance is impaired. Moreover, antifouling property cannot be imparted with a perfluoroalkyl group having 5 or less carbon atoms in the fluorinated monomer. On the other hand, since the perfluoroalkyl group having 6 carbon atoms does not have crystallinity, it can be uniformly dispersed when the fluorine-based block copolymer is oriented on the surface, and an excellent surface appearance can be obtained. Water and oil repellency can be secured.
In addition, the water / oil repellency of the fluorine-containing block copolymer is exhibited even when a low shrinkage agent is not used in combination, but the use of the low shrinkage agent together with the surface smoothness further improves the water repellency and water repellency. Oiliness is improved. The reason why a low polarity such as a polystyrene based low shrinkage agent is effective as this low shrinkage agent is that the fluorine-based block copolymer has a curable resin such as an unsaturated polyester resin due to the polarity due to the ester group. This is because the affinity is reduced and the fluorine-based block copolymer is easily segregated on the surface by using a low-polarity polystyrene-based low-shrink agent in combination with an affinity.

Claims (6)

A curable resin composition comprising a fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment, a curable resin, and a low shrinkage agent,
The fluorine-containing monomer constituting the fluorine-containing segment is a fluorine-containing monomer represented by the following general formula (I) having a C6 perfluoroalkyl group,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
The said low shrinkage | contraction agent is a polystyrene type, 1-150 weight part is contained with respect to 100 weight part of said curable resins, The curable resin composition characterized by the above-mentioned.

(In the general formula (I), R1 is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and R2 is an aliphatic group having 1 or more carbon atoms.) A curable resin composition comprising a fluorinated block copolymer comprising a fluorinated segment and a non-fluorinated segment, and a curable resin,
The fluorine-containing monomer constituting the fluorine-containing segment is a fluorine-containing monomer represented by the following general formula (I) having a C6 perfluoroalkyl group,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
A curable resin composition containing no low shrinkage agent.

(In the general formula (I), R1 is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and R2 is an aliphatic group having 1 or more carbon atoms.)   The curable resin composition according to claim 1 or 2, wherein the fluorine-containing segment of the fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment is 5 to 95% by weight.   The curing according to any one of claims 1 to 3, comprising 0.01 to 50 parts by weight of the fluorine-based block copolymer with respect to 100 parts by weight of the curable resin. Resin composition.   A curable resin cured product obtained by curing the curable resin composition according to any one of claims 1 to 4.   The cured product of the curable resin according to claim 5, which is obtained by thermoforming at the time of curing.