WO2008069239A1 - Resin molded product with high level of surface design and article having the resin molded product on its surface - Google Patents

Resin molded product with high level of surface design and article having the resin molded product on its surface Download PDF

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Publication number
WO2008069239A1
WO2008069239A1 PCT/JP2007/073500 JP2007073500W WO2008069239A1 WO 2008069239 A1 WO2008069239 A1 WO 2008069239A1 JP 2007073500 W JP2007073500 W JP 2007073500W WO 2008069239 A1 WO2008069239 A1 WO 2008069239A1
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WO
WIPO (PCT)
Prior art keywords
matrix
particles
epoxy resin
resin
resin molded
Prior art date
Application number
PCT/JP2007/073500
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroaki Shimomura
Yukio Naito
Toshio Kobayashi
Original Assignee
Toto Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toto Ltd. filed Critical Toto Ltd.
Publication of WO2008069239A1 publication Critical patent/WO2008069239A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention is a resin molded body used as a surface material of a member having heat resistance and a novel pattern, and more specifically, a sink, a wash basin, other water resistance, heat resistance, and design properties are required.
  • the present invention relates to a resin molded body used as a surface material of an article to be manufactured.
  • Japanese Patent Application Laid-Open No. 10-249860 discloses a product obtained by coloring particles obtained by pulverizing a marble-like synthetic resin product and adding the resin to a resin. Dairi Stone-like synthetic resin can be recycled, and the product has an opaque marble-like design.
  • JP-A-7-33500 discloses a compound in which transparent particles are blended with a resin. According to this publication, it is said that by blending transparent particles that are soluble in a matrix resin, a molded product having a deep texture and excellent strength can be obtained.
  • Japanese Patent Application Laid-Open No. 2004-250521 discloses a resin molded body in which nano-sized inorganic particles are blended. Here, the inorganic particles do not function as those forming the handle. Disclosure of the invention
  • An object of the present invention is to provide a resin molded article having excellent heat resistance while achieving a new pattern with particles.
  • the object of the present invention is to provide a resin molded body used as a surface material for sinks, washstands, and other articles that require water resistance, heat resistance, and design.
  • the resin molded body according to the present invention is a resin molded body comprising a matrix and particles dispersed in the matrix, wherein the matrix is made of an epoxy resin compound, and the particles are The epoxy resin composition having a composition different from that of the epoxy resin composition of the matrix and the surface of the water-based resin molded product as a reference line. It is characterized by having a let diameter of lmm or more.
  • FIG. 1 is a diagram showing a particle diameter measurement method.
  • FIG. 2 is a pyrolysis GC / MS chart of the matrix of Example 1.
  • FIG. 3 is a chart by pyrolysis GC / MS of the particles of Example 1.
  • FIG. 4 is a photograph showing the appearance of Example 3.
  • FIG. 5 is a photograph showing the appearance of Example 11.
  • FIG. 6 is a photograph showing the appearance of Comparative Example 4.
  • FIG. 7 is a schematic diagram showing an embodiment in which particles (2) are uniformly packed in a part of the matrix (1) and particles are not present in a part of the matrix.
  • FIG. 8 is a schematic view showing an embodiment in which particles (2) are uniformly heavy-filled throughout the matrix in the matrix (1).
  • the resin molded body according to the present invention has a novel handle made of particles and is excellent in heat resistance and the like, and is preferably used as a surface material for various members.
  • the resin molded body according to the present invention is excellent in water resistance, heat resistance and design, and as a result, it is used as a so-called water-based resin molded body.
  • it is used as a sink, a sink, a kitchen counter, Used as a surface material for counters, tables, bathtubs, and other articles that require water resistance, heat resistance, and design.
  • the resin molded body according to the present invention is excellent in transparency and can impart a deep texture to the member. Because of its transparency, for example, by coloring the back surface, the color appears to be transmitted, and a desired color can be easily imparted to the article. Furthermore, it is excellent in mechanical strength such as impact strength.
  • the resin molded body according to the present invention comprises a matrix and particles dispersed in the matrix, the matrix is made of an epoxy resin compound, and the particles are made of a Matritus epoxy resin compound. Consists of epoxy resin blends of different compositions. Specific examples of the epoxy resin composition constituting the matrix and particles will be described later.
  • the particles are in a dispersed state in the matrix.
  • the dispersion means that the particles are present uniformly and randomly in the matrix (for example, Fig. 8), and the matrix. It is used to include the case where the part is uniformly filled and the particle is not present in a part of the matrix (for example, Fig. 7).
  • the particles dispersed in the matrix have a ferret diameter of 1 mm or more with the resin molded body surface as a reference line.
  • the upper limit of the particle is usually set to be equal to or less than the film thickness of the resin molded body.
  • the particle ferret diameter is set to 30 mm or less. Particles of less than 1 mm are not preferred because the interface of the particles does not function as a handle in the resin molded product, and is simply translucent with light scattered.
  • This particle size is measured as follows. That is, first, when the resin molded body is cut into about 1 mm in the thickness direction, a cross section as shown in FIG. 1 is observed.
  • the ferret diameter 5 (Feret diameter) with the surface 3 of the compact as the reference line 4 is measured for 100 particles on the cut surface, and the particle diameter is calculated by taking a simple average.
  • the ferret diameter is defined as the distance between the leftmost tangent perpendicular to the reference line and the right tangent, and the length of the projected view of the particles along the given reference line.
  • the vertical tangent is a spring in the thickness direction.
  • the resin molded body according to the present invention basically includes a mixture of particles made of an epoxy resin compound having a composition different from that of the matrix in an epoxy resin compound, and after filling the mold into the mold, the calorie heat It can be gained by making it hard.
  • the particles in the present invention can be obtained by preparing a molded body of an epoxy resin compound in advance and pulverizing it. Since the epoxy resin compound is excellent in heat resistance, it can be melted by pulverization heat and fixed in the pulverizer with an ordinary pulverizer. Examples thereof include a crusher such as a jaw crusher, a hammer mill, a cutter mill, a wheelie powder mill, a pin minole, a roll mill, etc. After pulverization, the particles are classified by a vibration sieve or the like to obtain desired particles.
  • the method of molding the resin molded body according to the present invention is not particularly limited! /, But the casting method is preferred! /.
  • An epoxy resin compound serving as a matrix may be cast in a state where particles are previously placed in the mold, or a mixture of epoxy resin compound serving as a matrix and particles may be cast. After filling into the mold, it is cured by heating to 60-; 140 ° C. Thereafter, it is removed from the mold, and a resin molded body for water is obtained. If necessary, after-curing (for example, 100 to; heating at a temperature of about 180 ° C .; operation for heating for about 3 to 3 hours) may be performed.
  • the epoxy resin compound comprises an epoxy resin main component and a curing agent.
  • epoxy resin main agent examples include aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol nopolac type epoxy resin, and cresol nopolac type epoxy resin.
  • aliphatic epoxy resin examples include hydrogenated bisphenol A type epoxy resin, polyolefin type epoxy resin, and alicyclic epoxy resin.
  • epoxy resins include those having different degrees of polymerization, those imparted with flame retardancy by introducing halogen, those modified in various ways, and those copolymerized.
  • the curing agent examples include amine-based curing agents such as chain aliphatic amines such as ethylene diamine, diethylene triamine, hexamethylene diamine and the like, cyclic amines such as isophorone diamine and bis (aminomethyl). ) Cyclohexane, bis (4 amino-3-methylzinchexyl) methane, etc., and m-xylene diamine, metaphenylene diamine, diaminodiphenyl methane, etc. which are aromatic amines.
  • chain aliphatic amines such as ethylene diamine, diethylene triamine, hexamethylene diamine and the like
  • cyclic amines such as isophorone diamine and bis (aminomethyl).
  • Cyclohexane bis (4 amino-3-methylzinchexyl) methane, etc.
  • m-xylene diamine, metaphenylene diamine, diaminodiphenyl methane, etc. which are aromatic amines
  • Aliphatic acid anhydrides dodecenyl succinic anhydride, polyazibic acid anhydride, cycloaliphatic acid anhydrides, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , Anhydrous methyl hymic acid, etc., and aromatic anhydride Tal acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid and the like.
  • the particles are made of an epoxy resin compound having a composition different from that of the matrix epoxy resin compound.
  • the different composition means that the epoxy resin main component or curing agent of the epoxy resin compound of the particle is used in combination with a different one from that of the matrix, or the compound in which the proportion of the epoxy resin main agent or the curing agent is changed is used. That means.
  • the molecule or the cross-linked structure changes in the matrix and particles in the molded body, and as a result, a boundary line derived from the difference in refractive index occurs at the interface between the matrix and the particles.
  • the particles can be expressed as a pattern.
  • the transparency of the molded body is very high, for example, When particles are overlapped in the thickness direction in the trix, the boundary line generated at the interface between the particles and the matrix can be visually recognized for each particle, and they overlap to form a characteristic pattern.
  • the different composition may be different between the epoxy resin main component and the curing agent.
  • the epoxy resin base and curing agent are completely different between the matrix and particles, specifically, liquid bisphenol A type epoxy resin and ethylenediamine are used for the matrix, and bisphenol F type epoxy resin and isophorone diamine are used for the particles.
  • the epoxy resin base is a liquid bisphenol A type epoxy resin for both matrix and particles
  • the matrix is diaminodiphenylmethane.
  • the particles may be hexahydrophthalic anhydride.
  • the curing agent may be the same and the epoxy resin main component may be different, for example, both the curing agent is methylhexahydrophthalic anhydride, and the epoxy resin main component is a liquid bisphenol A type epoxy resin.
  • the particles may be alicyclic epoxy resins. It is also possible to use epoxy resin bases with different degrees of polymerization. For example, both the curing agent is methylhexahydrophthalic anhydride and the epoxy resin base is a liquid bisphenol A type epoxy resin.
  • the particles may be solid bisphenol A type epoxy resin.
  • the different composition may be obtained by changing the blending amount.
  • the matrix uses 100% bisphenol A type epoxy resin as the epoxy resin base, and the particles are 50% bisphenol A type epoxy resin.
  • the alicyclic epoxy resin may contain 50%.
  • the composition of both the epoxy resin main agent and the curing agent may be changed, or only the mixing ratio of the curing agent may be changed.
  • an aromatic epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin and an alicyclic epoxy resin or water are used as a combination of different epoxy resin main components.
  • a combination of aliphatic epoxy resins such as bisphenol A type epoxy resin is preferably used. This is because the difference in refractive index can be easily changed by the difference in concentration of the benzene rings.
  • a combination of an amine type and an acid anhydride type has a completely different structure, which is preferable, and even in the same amine type, a combination of a chain and a cyclic aliphatic amine and an aromatic amine, an alicyclic type and an aliphatic type.
  • Combinations of acid anhydrides and aromatic acid anhydrides are also preferred because it is easy to change the benzene ring concentration.
  • the difference in composition between the matrix and the particles can be measured by various analytical techniques.
  • Thermosetting resin moldings such as epoxy resins are insoluble and infusible, so analytical methods are limited. For example, when samples are taken from the matrix and particles of the molding and subjected to pyrolysis GC-MS. And a method of observing the position and intensity of the peak. The method can be selected as necessary, such as IR and solid N MR.
  • the particles when dispersed in a matrix, are sized so as to realize a particle having a ferret diameter of 1 mm or more with the resin molded body surface as a reference line.
  • the particles before being dispersed in the matrix preferably have a diameter of at least mm.
  • the matrix of the resin molded body according to the present invention may contain inorganic particles. However, since the presence of inorganic particles lowers the transparency of the resin molded body, the desired transparency is taken into consideration. And its abundance needs to be determined. According to a preferred embodiment of the present invention, the matrix is preferably substantially free of inorganic particles in order to achieve good transparency.
  • One embodiment of the present invention is characterized in that a coating portion is provided on the back surface of the water-borne resin molded body.
  • the resin molded body of the present invention has a high transparency such that the particle interfaces appear to overlap each other. Therefore, even if the same molded body is formed by providing the back surface with a painted portion, the color of the painted surface on the back surface. There is an advantage that the color can be easily changed by changing. In addition, there are cases in which it is not desired to show the storage and piping under the counter in the resin molding for water, and it is possible to conceal the under counter without damaging the new pattern by providing a coating part on the back side.
  • a blend was obtained by mixing 100 parts by weight of bisphenol A type epoxy resin, 86 parts by weight of methylhexahydrophthalic anhydride, and 3 parts by weight of quaternary ammonium salt as a curing accelerator. This was cast on a glass plate coated with a release agent and cured by heating at 90 ° C. for 2 hours and further at 140 ° C. for 2 hours to obtain a plate having a thickness of 15 mm. This is pulverized with a jaw crusher pulverizer, and the obtained particles are passed through a sieve with a mesh opening of 2 mm. Further, the particles remaining on the sieve are collected by passing through a lmm sieve to collect particles of 1 mm to 2 mm. Got.
  • a matrix resin was obtained by mixing 100 parts by weight of an alicyclic epoxy resin, 129 parts by weight of methylhexahydrophthalic anhydride, and 3 parts by weight of a quaternary ammonium salt as a curing accelerator.
  • the pulverized particles were mixed in the matrix resin at a ratio of 50 wt% and mixed. This mixture was poured into a release-molded glass mold and cured by heating at 90 ° C for 2 hours and further at 140 ° C for 2 hours to obtain a plate having a thickness of 15 mm. Here, when the obtained plate was observed, the particles were uniformly dispersed in the matrix resin.
  • blending the pulverized particles in the matrix resin at a ratio of 50 wt% means blending so that the ratio of the weight of the particles to the total weight of the matrix and particle mixture is 50 wt%. Also in the following examples, the blending ratio is a weight ratio.
  • Particles having a size of 2 to 3 mm were produced in the same manner as in Example 1, except that particles passing through a sieve having a mesh opening of 3 mm and remaining on the sieve having a mesh opening of 2 mm were collected.
  • the obtained matrix resin was mixed with pulverized particles at a ratio of 50 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 20 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • a matrix resin was obtained in the same manner as in Example 2.
  • the obtained matrix resin was mixed with pulverized particles at a ratio of 5 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 5 mm.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 30 mm.
  • Particles having a size of 10 to 15 mm were produced in the same manner as in Example 1 except that particles passing through a sieve having a mesh size of 15 mm and remaining on the sieve having a mesh size of 10 mm were collected.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 30 mm.
  • the obtained matrix resin was blended with pulverized particles in a proportion of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • a blue urethane paint was sprayed on the back of the plate.
  • the main component is a reactive curable resin that is not an epoxy.
  • the resulting matrix resin is blended with pulverized particles in a proportion of 50 wt%, and the mixture is cast into a release-molded glass mold and heated and cured at 25 ° C for 6 hours and further at 50 ° C for 1 hour. A plate with a thickness of 15 mm was obtained.
  • PMMA pellets cut to 3 mm length were used. That is, the PMMA pellet used is a thermoplastic resin.
  • PMMA pellets particles were blended in a ratio of 50 wt% to the obtained matrix resin, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • PMMA pellets cut to 3 mm length were used.
  • a matrix resin was obtained in the same manner as in Example 2.
  • PMMA pellets particles were blended at a ratio of 20 wt% to the obtained matrix resin, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • Particles having a size of 0.1 mm or less were produced in the same manner as in Example 1 except that the particles dropped under the sieve having a mesh opening of 0.1 mm were collected.
  • the obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
  • the difference in composition between the matrix and the particles was examined by the following method.
  • the molded body was cut to a thickness of 1 mm in the thickness direction to make it easy to recognize the matrix and particles.
  • Samples of 0.5 mg from the matrix and 0.5 mg from the particles were taken, respectively. This was analyzed by pyrolysis GC MS. The analysis conditions were as shown in Table 1.
  • Fig. 2 The results of pyrolysis GC-MS analysis for Example 1 are shown in Fig. 2 for the matrix and Fig. 3 for the particles.
  • the vertical axis represents the detected signal intensity
  • the horizontal axis represents the retention time.
  • the scales on the horizontal axis in Figs. 2 and 3 are aligned so that the peak positions can be easily compared.
  • the matrix results show a peak derived from the bisphenol A type epoxy resin and no peak derived from the alicyclic epoxy resin.
  • the alicyclic epoxy resin peak appears in the particle results, and there is no peak derived from the BPA type epoxy resin.
  • the appearance change of the compact surface was evaluated according to the following criteria.
  • haze-gard plus manufactured by BY gardner
  • BY gardner was used to measure the total light transmittance in a light source including a 550 nm light beam in the thickness direction of the molded body.
  • the painted part was cut or sanded to measure the gloss finish.
  • the thickness was 15 mm or less, and when the thickness was more than this, it was cut or scraped to a thickness of 15 mm or less, and the gloss finish was measured.
  • the molded body was placed in a plane so that the surface was on the upper surface, and the appearance was visually observed from above in the room, and evaluation was performed according to the following criteria.
  • O The outline of the particle appears as a pattern.
  • the particle size was measured as follows. That is, the compact is cut as thin as about 1 mm in the thickness direction, and the ferret diameter (Feret diameter) with the surface of the compact as the reference line is measured for 100 particles on the cut surface! The simple average was taken as the particle size.
  • the resin molded bodies of Examples 1 to 11 are also excellent in transparency and pattern.
  • Comparative Example 2 even if the matrix resin is an epoxy resin compound, if acrylic particles with low heat resistance are used as the compounded particles, the acrylic particles exposed on the surface themselves are deformed by heat and cause a change in appearance. Indicates rubbing.
  • the epoxy resin composition since the epoxy resin composition generates heat and cure shrinkage during curing, whitening of the acrylic particle interface, which is thought to be due to this effect, occurred, and the transparency and handle were not satisfactory.
  • the resin molded body of Comparative Example 3 was obtained by reducing the blending amount of the particles to 20%, forming no layer of acrylic particles in the vicinity of the surface of the molded body, and forming a matrix only of the epoxy resin blend.
  • Examples:! To 3 and 9 show that the power of changing the pattern when the particle size is changed Transparency and the sharpness of the pattern are ensured! /.
  • a photograph of the molded product of Example 3 is shown in FIG.
  • a photograph of the molded product of Example 11 is shown in FIG. 5, and a photograph of the molded product of Comparative Example 4 is shown in FIG. Comparing the two, it can be seen that when the particle is 0.1 mm or less as in Comparative Example 4, the particle interface cannot be visually recognized as a handle, and the force does not function as a handle.
  • the resin molded body of Comparative Example 5 in which the particles and the matrix have exactly the same composition has high transparency with a total light transmittance of 90.5%, but there is almost no difference in the refractive index between the particles and the matrix resin. Became very visible, and the sharpness of the pattern was not sufficient.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention provides a resin molded product having excellent heat resistance and other properties while realizing a novel pattern formed of particles. The resin molded product comprises a matrix and particles dispersed into the matrix and is characterized in that the matrix is formed of an epoxy resin formulation, and the particles is formed of an epoxy resin formulation having a composition different from the epoxy resin formulation in the matrix and has a size of not less than 1 mm in terms of a Feret's diameter using the surface of the resin molded product for a wet area as a ground line. The resin molded product is used as a surface material for sinks, washing stands, and other article required to have water resistance, heat resistance, and a high level of design.

Description

明 細 書  Specification
表面意匠性を備えた樹脂成形体およびそれを表面に有した物品 技術分野  RESIN MOLDED BODY WITH SURFACE DESIGN AND GOODS HAVING SAME
[0001] 本発明は、耐熱性および新規な柄を備えた、部材の表面材料として用いられる樹 脂成形体、詳細には流し、洗面台、その他の耐水性、耐熱性、そして意匠性が求め られる物品の表面材料として用いられる樹脂成形体に関する。  [0001] The present invention is a resin molded body used as a surface material of a member having heat resistance and a novel pattern, and more specifically, a sink, a wash basin, other water resistance, heat resistance, and design properties are required. The present invention relates to a resin molded body used as a surface material of an article to be manufactured.
背景技術  Background art
[0002] 近年、粒子を樹脂に配合することで様々な意匠を有する樹脂成形体が提案されて いる。例えば、特開平 10— 249860号公報には、大理石調の合成樹脂製品を粉砕 して得られた粒子を着色し、これを樹脂に加え成型したものが開示されている。大理 石調の合成樹脂のリサイクルを図ることができ、製品は不透明な大理石調の意匠を 有する。  In recent years, resin molded bodies having various designs have been proposed by blending particles into a resin. For example, Japanese Patent Application Laid-Open No. 10-249860 discloses a product obtained by coloring particles obtained by pulverizing a marble-like synthetic resin product and adding the resin to a resin. Dairi Stone-like synthetic resin can be recycled, and the product has an opaque marble-like design.
[0003] また、特開平 7— 33500号公報には、透明な粒子を樹脂に配合したものが開示さ れている。この公報によれば、マトリックスとなる樹脂に対して溶解性を持つ透明粒子 を配合することで、深みのある質感を出しながら、その強度にも優れる成形体が得ら れるとされている。  [0003] Also, JP-A-7-33500 discloses a compound in which transparent particles are blended with a resin. According to this publication, it is said that by blending transparent particles that are soluble in a matrix resin, a molded product having a deep texture and excellent strength can be obtained.
[0004] また、特開 2004— 250521号公報は、ナノサイズの無機粒子を配合した樹脂成形 体を開示している。ここで、無機粒子は柄を形成するものとしては機能していない。 発明の開示  [0004] Japanese Patent Application Laid-Open No. 2004-250521 discloses a resin molded body in which nano-sized inorganic particles are blended. Here, the inorganic particles do not function as those forming the handle. Disclosure of the invention
[0005] 本発明は、粒子による新規な柄を達成しながら、耐熱性等にも優れた樹脂成形体 の提供をその目的としている。とりわけ本発明は、流し、洗面台、その他の耐水性、耐 熱性、そして意匠性が求められる物品の表面材料として用いられる樹脂成形体の提 供をその目的としている。  [0005] An object of the present invention is to provide a resin molded article having excellent heat resistance while achieving a new pattern with particles. In particular, the object of the present invention is to provide a resin molded body used as a surface material for sinks, washstands, and other articles that require water resistance, heat resistance, and design.
[0006] そして、本発明による樹脂成形体は、マトリックスと、前記マトリックス中に分散された 粒子とを含んでなる樹脂成形体であって、前記マトリックスがエポキシ樹脂配合物か らなり、前記粒子が、前記マトリックスのエポキシ樹脂配合物とは異なる組成のェポキ シ樹脂配合物より構成されかつ前記水回り用樹脂成形体の表面を基準線としたフエ レット径で lmm以上の大きさを有するものであることを特徴とする。 [0006] The resin molded body according to the present invention is a resin molded body comprising a matrix and particles dispersed in the matrix, wherein the matrix is made of an epoxy resin compound, and the particles are The epoxy resin composition having a composition different from that of the epoxy resin composition of the matrix and the surface of the water-based resin molded product as a reference line. It is characterized by having a let diameter of lmm or more.
図面の簡単な説明  Brief Description of Drawings
[0007] [図 1]粒子径の計測方法を示した図である。  [0007] FIG. 1 is a diagram showing a particle diameter measurement method.
[図 2]実施例 1のマトリックスの熱分解 GC/MSによるチャートである。  FIG. 2 is a pyrolysis GC / MS chart of the matrix of Example 1.
[図 3]実施例 1の粒子の熱分解 GC/MSによるチャートである。  FIG. 3 is a chart by pyrolysis GC / MS of the particles of Example 1.
[図 4]実施例 3の外観を示した写真である。  FIG. 4 is a photograph showing the appearance of Example 3.
[図 5]実施例 11の外観を示した写真である。  FIG. 5 is a photograph showing the appearance of Example 11.
[図 6]比較例 4の外観を示した写真である。  FIG. 6 is a photograph showing the appearance of Comparative Example 4.
[図 7]マトリックス（1)中に、粒子（2)が、マトリックスの一部に均一に充填され、マトリツ タスの一部には粒子が存在しない態様を示した模式図である。  FIG. 7 is a schematic diagram showing an embodiment in which particles (2) are uniformly packed in a part of the matrix (1) and particles are not present in a part of the matrix.
[図 8]マトリックス（1)中に、粒子（2)が、マトリックス全体にわたって均一に重充填され た態様を示した模式図である。  FIG. 8 is a schematic view showing an embodiment in which particles (2) are uniformly heavy-filled throughout the matrix in the matrix (1).
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0008] 本発明による樹脂成形体は、粒子による新規な柄を有し、耐熱性等にも優れるもの であり、様々な部材の表面材料として好ましく用いられる。本発明による樹脂成形体 は、耐水性、耐熱性、そして意匠性に優れるものであり、その結果、いわゆる水回り用 樹脂成形体として用いられ、具体的には、流し、洗面台、キッチンカウンター、カウン ター、テーブル、浴槽、その他の耐水性、耐熱性、そして意匠性が求められる物品の 表面材料として用いられる。また、本発明による樹脂成形体は、透明性に優れ、深み のある質感を部材に付与することが可能となる。その透明性ゆえ、例えば裏面を着色 することで、その色が透過して見え、容易に所望の色を物品に付与することが可能と なる。さらに、その衝撃強度等の機械的強度にも優れたものである。  [0008] The resin molded body according to the present invention has a novel handle made of particles and is excellent in heat resistance and the like, and is preferably used as a surface material for various members. The resin molded body according to the present invention is excellent in water resistance, heat resistance and design, and as a result, it is used as a so-called water-based resin molded body. Specifically, it is used as a sink, a sink, a kitchen counter, Used as a surface material for counters, tables, bathtubs, and other articles that require water resistance, heat resistance, and design. Further, the resin molded body according to the present invention is excellent in transparency and can impart a deep texture to the member. Because of its transparency, for example, by coloring the back surface, the color appears to be transmitted, and a desired color can be easily imparted to the article. Furthermore, it is excellent in mechanical strength such as impact strength.
[0009] 本発明による樹脂成形体は、マトリックスと、そのマトリックス中に分散された粒子を 含んでなるものであり、マトリックスはエポキシ樹脂配合物からなり、また粒子はマトリツ タスのエポキシ樹脂配合物とは異なる組成のエポキシ樹脂配合物からなる。マトリック スおよび粒子を構成するエポキシ樹脂配合物の具体例は後記する。  [0009] The resin molded body according to the present invention comprises a matrix and particles dispersed in the matrix, the matrix is made of an epoxy resin compound, and the particles are made of a Matritus epoxy resin compound. Consists of epoxy resin blends of different compositions. Specific examples of the epoxy resin composition constituting the matrix and particles will be described later.
[0010] マトリックス中において粒子は分散された状態にあり、ここで分散とは、マトリックス中 にランダムに均一に粒子が存在している場合（例えば、図 8)に加え、マトリックスの一 部に均一に充填され、マトリックスの一部には粒子が存在しない場合 (例えば、図 7) も含む意味に用いる。 [0010] The particles are in a dispersed state in the matrix. Here, the dispersion means that the particles are present uniformly and randomly in the matrix (for example, Fig. 8), and the matrix. It is used to include the case where the part is uniformly filled and the particle is not present in a part of the matrix (for example, Fig. 7).
[0011] 本発明において、マトリックスに分散される粒子は、樹脂成形体表面を基準線とした フェレット径で lmm以上の大きさを有するものとされる。粒子の上限は樹脂成形体の 膜厚以下とされるのが通常であり、例えば、膜厚 30mmの樹脂成形体にあっては粒 子のフェレット径は 30mm以下とされる。 1mm未満の粒子では、樹脂成形体におい て粒子の界面が柄として機能せず、単に光が散乱した半透明のものとなるため好まし くない。この粒子径は以下のように測定される。すなわち、まず、樹脂成形体を厚み 方向に lmm程度に薄く切断すると、図 1に示されるような断面が観察される。成形体 の表面 3を基準線 4としたときのフェレット径 5 (Feret径）を切断面にある 100個の粒 子について計測し、単純平均をとることで粒子径を計算する。ここでフェレット径とは、 基準線に垂直な最も左の接線と右の接線の間の距離として、与えられた基準線に沿 つた粒子の投影図の長さとして定義されるものである。ここで垂直な接線とは厚み方 向の泉のことである。  In the present invention, the particles dispersed in the matrix have a ferret diameter of 1 mm or more with the resin molded body surface as a reference line. The upper limit of the particle is usually set to be equal to or less than the film thickness of the resin molded body. For example, in a resin molded body having a film thickness of 30 mm, the particle ferret diameter is set to 30 mm or less. Particles of less than 1 mm are not preferred because the interface of the particles does not function as a handle in the resin molded product, and is simply translucent with light scattered. This particle size is measured as follows. That is, first, when the resin molded body is cut into about 1 mm in the thickness direction, a cross section as shown in FIG. 1 is observed. The ferret diameter 5 (Feret diameter) with the surface 3 of the compact as the reference line 4 is measured for 100 particles on the cut surface, and the particle diameter is calculated by taking a simple average. Here, the ferret diameter is defined as the distance between the leftmost tangent perpendicular to the reference line and the right tangent, and the length of the projected view of the particles along the given reference line. Here, the vertical tangent is a spring in the thickness direction.
[0012] 本発明による樹脂成形体は、基本的には、エポキシ樹脂配合物中に、マトリックスと 異なる組成のエポキシ樹脂配合物からなる粒子を混合し、これを型内に充填したの ちカロ熱硬ィ匕させることによって得ること力できる。  [0012] The resin molded body according to the present invention basically includes a mixture of particles made of an epoxy resin compound having a composition different from that of the matrix in an epoxy resin compound, and after filling the mold into the mold, the calorie heat It can be gained by making it hard.
[0013] 本発明における粒子は、エポキシ樹脂配合物による成形体を予め作製し、粉砕す ることで得られる。エポキシ樹脂配合物は耐熱性に優れているため、粉砕熱により融 解して粉砕機内に固着することはなぐ通常の粉砕機で可能である。例えば、ジョー クラッシャー、ハンマーミル、カッターミル、ウィレー粉碎機、ピンミノレ、ロールミル等の 粉砕機が挙げられ、粉砕した後、振動篩等で分級し所望の粒子を得る。  [0013] The particles in the present invention can be obtained by preparing a molded body of an epoxy resin compound in advance and pulverizing it. Since the epoxy resin compound is excellent in heat resistance, it can be melted by pulverization heat and fixed in the pulverizer with an ordinary pulverizer. Examples thereof include a crusher such as a jaw crusher, a hammer mill, a cutter mill, a wheelie powder mill, a pin minole, a roll mill, etc. After pulverization, the particles are classified by a vibration sieve or the like to obtain desired particles.
[0014] 本発明による樹脂成形体の成形方法は特に限定されな!/、が、注型法が好まし!/、。  [0014] The method of molding the resin molded body according to the present invention is not particularly limited! /, But the casting method is preferred! /.
型内に予め粒子を入れた状態でマトリックスとなるエポキシ樹脂配合物を注型しても よぐまたマトリックスとなるエポキシ樹脂配合物と粒子を混合したものを注型してもよ い。型内に充填した後、これを 60〜； 140°Cに加熱して硬化させる。その後、型から取 り出し、水回り用樹脂成形体が得られる。必要に応じてアフターキュア（例えば、 100 〜； 180°C程度の温度で、；!〜 3時間程度加熱する操作)を行ってもよい。 [0015] 本発明にお!/、て、エポキシ樹脂配合物とはエポキシ樹脂主剤と硬化剤からなる。 An epoxy resin compound serving as a matrix may be cast in a state where particles are previously placed in the mold, or a mixture of epoxy resin compound serving as a matrix and particles may be cast. After filling into the mold, it is cured by heating to 60-; 140 ° C. Thereafter, it is removed from the mold, and a resin molded body for water is obtained. If necessary, after-curing (for example, 100 to; heating at a temperature of about 180 ° C .; operation for heating for about 3 to 3 hours) may be performed. [0015] In the present invention, the epoxy resin compound comprises an epoxy resin main component and a curing agent.
[0016] エポキシ樹脂主剤としては、例えば、芳香族系エポキシ樹脂として、ビスフエノール A型エポキシ樹脂、ビスフエノール F型エポキシ樹脂、フエノールノポラック型エポキシ 樹脂、クレゾールノポラック型エポキシ樹脂等が挙げられ、脂肪族系エポキシ樹脂と して、水添ビスフエノール A型エポキシ樹脂、ポリオレフイン型エポキシ樹脂、脂環式 エポキシ樹脂等が挙げられる。さらにはエポキシ樹脂には、重合度の異なるもの、ハ ロゲンを導入して難燃性を付与したもの、各種変性したもの、共重合したもの等も含 よれ 。 Examples of the epoxy resin main agent include aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol nopolac type epoxy resin, and cresol nopolac type epoxy resin. Examples of the aliphatic epoxy resin include hydrogenated bisphenol A type epoxy resin, polyolefin type epoxy resin, and alicyclic epoxy resin. Furthermore, epoxy resins include those having different degrees of polymerization, those imparted with flame retardancy by introducing halogen, those modified in various ways, and those copolymerized.
[0017] 硬化剤としては、例えば、アミン系硬化剤として、鎖状脂肪族ァミンであるエチレン ジァミン、ジエチレントリァミン、へキサメチレンジァミン等や、環状ァミンであるイソフォ ロンジァミン、ビス（アミノメチル）シクロへキサン、ビス（4 アミノー 3—メチルジンクロ へキシル)メタン等、さらには芳香族ァミンである m キシレンジァミン、メタフエ二レン ジァミン、ジアミノジフエニルメタン等が挙げられ、酸無水物系硬化剤として、脂肪族 酸無水物であるドデセニル無水コハク酸、ポリアジビン酸無水物や、脂環式酸無水 物であるテトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、へキサヒドロ無水 フタル酸、メチルへキサヒドロ無水フタル酸、無水メチルハイミック酸等、さらには芳香 族酸無水物である無水フタル酸、無水トリメット酸、無水ピロメリット酸、ベンゾフエノン テトラカルボン酸等が挙げられる。  Examples of the curing agent include amine-based curing agents such as chain aliphatic amines such as ethylene diamine, diethylene triamine, hexamethylene diamine and the like, cyclic amines such as isophorone diamine and bis (aminomethyl). ) Cyclohexane, bis (4 amino-3-methylzinchexyl) methane, etc., and m-xylene diamine, metaphenylene diamine, diaminodiphenyl methane, etc. which are aromatic amines. Aliphatic acid anhydrides, dodecenyl succinic anhydride, polyazibic acid anhydride, cycloaliphatic acid anhydrides, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , Anhydrous methyl hymic acid, etc., and aromatic anhydride Tal acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid and the like.
[0018] 本発明にお!/、て、粒子は、マトリックスのエポキシ樹脂配合物とは異なる組成のェ ポキシ樹脂配合物からなる。異なる組成とは、粒子のエポキシ樹脂配合物のェポキ シ樹脂主剤または硬化剤をマトリックスのそれとは違うものを組み合わせて用いる、あ るいはエポキシ樹脂主剤また硬化剤の配合割合を変えた配合物を用いることを意味 する。これにより、成形体中のマトリックスと粒子では、分子あるいは架橋構造が変化 し、その結果このマトリックスと粒子との界面では屈折率差に由来する境界線が生じ る。つまり、優れた耐熱性を持つエポキシ樹脂をマトリックスおよび粒子いずれにも使 用しながら、組成を異ならせることで成形体の屈折率差を積極的に利用することが可 能となる。これにより、マトリックスと粒子とで色や透明性に差がほとんどない場合でも 粒子を柄として表現できる。また、成形体の透明性が非常に高いことから、例えば、マ トリックス中で厚み方向に粒子が重なって存在しているとき、粒子とマトリックスとの界 面に生じる境界線がいずれの粒子についても視認でき、それらが重なって特徴的な 柄となる。 [0018] In the present invention, the particles are made of an epoxy resin compound having a composition different from that of the matrix epoxy resin compound. The different composition means that the epoxy resin main component or curing agent of the epoxy resin compound of the particle is used in combination with a different one from that of the matrix, or the compound in which the proportion of the epoxy resin main agent or the curing agent is changed is used. That means. As a result, the molecule or the cross-linked structure changes in the matrix and particles in the molded body, and as a result, a boundary line derived from the difference in refractive index occurs at the interface between the matrix and the particles. In other words, it is possible to positively utilize the difference in refractive index of the molded article by using different epoxy resins having excellent heat resistance for both the matrix and the particles while changing the composition. As a result, even when there is almost no difference in color and transparency between the matrix and the particles, the particles can be expressed as a pattern. In addition, since the transparency of the molded body is very high, for example, When particles are overlapped in the thickness direction in the trix, the boundary line generated at the interface between the particles and the matrix can be visually recognized for each particle, and they overlap to form a characteristic pattern.
[0019] 従って、異なる組成とは、エポキシ樹脂主剤と硬化剤とにおいて異なるものであって もよい。例えば、エポキシ樹脂主剤と硬化剤がマトリックスと粒子で全く違う場合、具 体的には、マトリックスに液状ビスフエノール A型エポキシ樹脂とエチレンジァミンを、 粒子にはビスフエノール F型エポキシ樹脂とイソフォロンジァミンであってもよい。また 、エポキシ樹脂主剤は同一で、硬化剤のみ異なるものとしてもよぐ例えば、マトリック スおよび粒子ともにエポキシ樹脂主剤は液状ビスフエノール A型エポキシ樹脂であり 、硬化剤がマトリックスはジアミノジフエニルメタンであり、粒子がへキサヒドロ無水フタ ル酸であってもよい。さらに、硬化剤は同一でエポキシ樹脂主剤が異なる場合であつ てもよく、例えば、硬化剤はともにメチルへキサヒドロ無水フタル酸であり、エポキシ樹 脂主剤がマトリックスは液状ビスフエノール A型エポキシ樹脂であり、粒子が脂環式ェ ポキシ樹脂であってもよい。また、重合度の違うエポキシ樹脂主剤を使用した場合で あってもよく、例えば、硬化剤はともにメチルへキサヒドロ無水フタル酸であり、ェポキ シ樹脂主剤がマトリックスは液状ビスフエノール A型エポキシ樹脂であり、粒子が固形 ビスフエノール A型エポキシ樹脂であってもよい。  Therefore, the different composition may be different between the epoxy resin main component and the curing agent. For example, if the epoxy resin base and curing agent are completely different between the matrix and particles, specifically, liquid bisphenol A type epoxy resin and ethylenediamine are used for the matrix, and bisphenol F type epoxy resin and isophorone diamine are used for the particles. Min. For example, the epoxy resin base is a liquid bisphenol A type epoxy resin for both matrix and particles, and the matrix is diaminodiphenylmethane. The particles may be hexahydrophthalic anhydride. Furthermore, the curing agent may be the same and the epoxy resin main component may be different, for example, both the curing agent is methylhexahydrophthalic anhydride, and the epoxy resin main component is a liquid bisphenol A type epoxy resin. The particles may be alicyclic epoxy resins. It is also possible to use epoxy resin bases with different degrees of polymerization. For example, both the curing agent is methylhexahydrophthalic anhydride and the epoxy resin base is a liquid bisphenol A type epoxy resin. The particles may be solid bisphenol A type epoxy resin.
[0020] さらに、異なる組成とは、配合量を変えたものであってもよい。例えば、硬化剤として はいずれもへキサヒドロ無水フタル酸を使用しながら、マトリックスはエポキシ樹脂主 剤にビスフエノール A型エポキシ樹脂を 100%使用し、粒子はビスフエノール A型ェ ポキシ樹脂が 50%、脂環式エポキシ樹脂が 50%の配合とするものであってもよい。 さらに、エポキシ樹脂主剤と硬化剤ともに配合を変える、硬化剤の配合比のみを変え るものであってもよい。  [0020] Further, the different composition may be obtained by changing the blending amount. For example, while using hexahydrophthalic anhydride as the curing agent, the matrix uses 100% bisphenol A type epoxy resin as the epoxy resin base, and the particles are 50% bisphenol A type epoxy resin. The alicyclic epoxy resin may contain 50%. Furthermore, the composition of both the epoxy resin main agent and the curing agent may be changed, or only the mixing ratio of the curing agent may be changed.
[0021] 本発明の好ましい態様によれば、エポキシ樹脂主剤の違うものの組み合わせとして 、ビスフエノール A型エポキシ樹脂やビスフエノール F型エポキシ樹脂のような芳香族 系エポキシ樹脂と脂環式エポキシ樹脂や水添ビスフエノール A型エポキシ樹脂のよう な脂肪族系エポキシ樹脂の組み合わせが好ましく用いられる。この組み合わせにあ つては、ベンゼン環の濃度差により屈折率差を容易に変化できるからである。また、 硬化剤についても、ァミン系と酸無水物系の組み合わせでは全く構造が異なるため 好ましぐまた同じアミン系でも鎖状および環状脂肪族ァミンと芳香族ァミンの組み合 わせ、脂環式や脂肪族酸無水物と芳香族酸無水物の組み合わせもベンゼン環濃度 を変えることが容易であり好ましレ、。 [0021] According to a preferred embodiment of the present invention, an aromatic epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin and an alicyclic epoxy resin or water are used as a combination of different epoxy resin main components. A combination of aliphatic epoxy resins such as bisphenol A type epoxy resin is preferably used. This is because the difference in refractive index can be easily changed by the difference in concentration of the benzene rings. Also, As for the curing agent, a combination of an amine type and an acid anhydride type has a completely different structure, which is preferable, and even in the same amine type, a combination of a chain and a cyclic aliphatic amine and an aromatic amine, an alicyclic type and an aliphatic type. Combinations of acid anhydrides and aromatic acid anhydrides are also preferred because it is easy to change the benzene ring concentration.
[0022] マトリックスと粒子の組成の違いは、各種分析手法により測定できる。エポキシ樹脂 のような熱硬化性樹脂の成形体は不溶不融であるため分析手法は限られる力 例え ば、成形体のマトリックスおよび粒子それぞれからサンプルを採取して、熱分解 GC— MSにかけた時のピークの位置や強度を観察する手法等が挙げられる。 IRや固体 N MR等必要に応じて手法を選択すればよい。  [0022] The difference in composition between the matrix and the particles can be measured by various analytical techniques. Thermosetting resin moldings such as epoxy resins are insoluble and infusible, so analytical methods are limited. For example, when samples are taken from the matrix and particles of the molding and subjected to pyrolysis GC-MS. And a method of observing the position and intensity of the peak. The method can be selected as necessary, such as IR and solid N MR.
[0023] 本発明において、粒子は、マトリックスに分散されたとき、樹脂成形体表面を基準線 としたフェレット径で lmm以上の大きさを有するものを実現する大きさとされる。実際 上は、マトリックスに分散される前の粒子はその径カ mm以上であることが好ましい。  [0023] In the present invention, when dispersed in a matrix, the particles are sized so as to realize a particle having a ferret diameter of 1 mm or more with the resin molded body surface as a reference line. In practice, the particles before being dispersed in the matrix preferably have a diameter of at least mm.
[0024] 本発明による樹脂成形体のマトリックスは、無機粒子を含んでいてもよいが、無機粒 子の存在は樹脂成形体の透明性を低下させるものであるから、所望の透明性を勘案 して、その存在量を定める必要がある。本発明の好ましい態様によれば、良好な透明 性を実現させるため、マトリックスは無機粒子を実質的に含まないものであることが好 ましい。  [0024] The matrix of the resin molded body according to the present invention may contain inorganic particles. However, since the presence of inorganic particles lowers the transparency of the resin molded body, the desired transparency is taken into consideration. And its abundance needs to be determined. According to a preferred embodiment of the present invention, the matrix is preferably substantially free of inorganic particles in order to achieve good transparency.
[0025] 本発明の一形態は前記水回り用樹脂成形体の裏面に塗装部を備えることを特徴と する。  [0025] One embodiment of the present invention is characterized in that a coating portion is provided on the back surface of the water-borne resin molded body.
本発明の樹脂成形体は、粒子の界面が重なって見えるという透明性の高さを備え ており、よって、裏面に塗装部を持たせることで同じ成形体であっても裏面の塗装部 の色を変えることで容易に色替えが可能である利点がある。また、水回り用樹脂成形 体において、カウンター下の収納や配管を見せたくない場合があり、裏面に塗装部を 設けることで新規な柄を損なうことなぐカウンター下を隠蔽することが可能となる。 実施例  The resin molded body of the present invention has a high transparency such that the particle interfaces appear to overlap each other. Therefore, even if the same molded body is formed by providing the back surface with a painted portion, the color of the painted surface on the back surface. There is an advantage that the color can be easily changed by changing. In addition, there are cases in which it is not desired to show the storage and piping under the counter in the resin molding for water, and it is possible to conceal the under counter without damaging the new pattern by providing a coating part on the back side. Example
[0026] 以下に実施例をあげて、本発明をより具体的に説明する。しかし、本発明はこれら 実施例に限定されるものではない。  [0026] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
[0027] 実施例 1 (1)粒子 [0027] Example 1 (1) Particle
ビスフエノール A型エポキシ樹脂 100重量部、メチルへキサヒドロ無水フタル酸 86 重量部、および硬化促進剤として 4級アンモニゥム塩 3重量部を混合し、配合物を得 た。これを、離型剤を塗布したガラス板に注型し、 90°Cで 2時間、さらに 140°Cで 2時 間加熱硬化させることで、厚さ 15mmの板を得た。これを、ジョークラッシャー粉砕機 にて粉砕し、得られた粒子を目開き 2mmの篩にかけて通過したものをさらに lmmの 篩にかけて篩上に残った粒子を捕集することで、 lmm〜2mmの粒子を得た。  A blend was obtained by mixing 100 parts by weight of bisphenol A type epoxy resin, 86 parts by weight of methylhexahydrophthalic anhydride, and 3 parts by weight of quaternary ammonium salt as a curing accelerator. This was cast on a glass plate coated with a release agent and cured by heating at 90 ° C. for 2 hours and further at 140 ° C. for 2 hours to obtain a plate having a thickness of 15 mm. This is pulverized with a jaw crusher pulverizer, and the obtained particles are passed through a sieve with a mesh opening of 2 mm. Further, the particles remaining on the sieve are collected by passing through a lmm sieve to collect particles of 1 mm to 2 mm. Got.
(2)マトリックス樹脂  (2) Matrix resin
脂環式エポキシ樹脂 100重量部、メチルへキサヒドロ無水フタル酸 129重量部、お よび硬化促進剤として 4級アンモニゥム塩 3重量部を混合して、マトリックス樹脂を得 た。  A matrix resin was obtained by mixing 100 parts by weight of an alicyclic epoxy resin, 129 parts by weight of methylhexahydrophthalic anhydride, and 3 parts by weight of a quaternary ammonium salt as a curing accelerator.
(3)成形体  (3) Molded body
上記マトリックス樹脂に、上記粉砕粒子を 50wt%の割合で配合し、混合した。この 混合物を離型処理したガラス型に注型し、 90°Cで 2時間、さらに 140°Cで 2時間加熱 硬化して、厚さ 15mmの板を得た。ここで、得られた板を観察すると、粒子はマトリック ス樹脂中に均一に分散していた。なおここで、粉砕粒子を 50wt%の割合でマトリック ス樹脂に配合するとは、マトリックスと粒子の混合物全体重量に占める粒子の重量の 割合が 50wt%となるように配合することを意味する。以下の実施例においても配合 割合は重量比である。  The pulverized particles were mixed in the matrix resin at a ratio of 50 wt% and mixed. This mixture was poured into a release-molded glass mold and cured by heating at 90 ° C for 2 hours and further at 140 ° C for 2 hours to obtain a plate having a thickness of 15 mm. Here, when the obtained plate was observed, the particles were uniformly dispersed in the matrix resin. Here, blending the pulverized particles in the matrix resin at a ratio of 50 wt% means blending so that the ratio of the weight of the particles to the total weight of the matrix and particle mixture is 50 wt%. Also in the following examples, the blending ratio is a weight ratio.
実施例 2  Example 2
(1)粒子  (1) Particle
目開き 3mmの篩を通過し目開き 2mmの篩上に残った粒子を捕集した以外は、実 施例 1と同様にして、 2〜3mmの粒子を製造した。  Particles having a size of 2 to 3 mm were produced in the same manner as in Example 1, except that particles passing through a sieve having a mesh opening of 3 mm and remaining on the sieve having a mesh opening of 2 mm were collected.
(2)マトリックス樹脂  (2) Matrix resin
ビスフエノール A型エポキシ樹脂 50重量部、脂環式エポキシ樹脂 50重量部、メチ ルへキサヒドロ無水フタル酸 108重量部、および硬化促進剤として 4級アンモニゥム 塩 3重量部を混合して、マトリックス樹脂を得た。  Mix 50 parts by weight of bisphenol A epoxy resin, 50 parts by weight of alicyclic epoxy resin, 108 parts by weight of methylhexahydrophthalic anhydride, and 3 parts by weight of quaternary ammonium salt as a curing accelerator. Obtained.
(3)成形体 得られたマトリックス樹脂に粉砕粒子を 50wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。 (3) Molded body The obtained matrix resin was blended with pulverized particles at a ratio of 50 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0029] 実施例 3 [0029] Example 3
(1)粒子  (1) Particle
目開き 6mmの篩を通過し目開き 4mmの篩上に残った粒子を捕集した以外は、実 施例 1と同様にして、 4〜6mmの粒子を製造した。  4 to 6 mm particles were produced in the same manner as in Example 1 except that particles passing through a 6 mm sieve and remaining on the 4 mm sieve were collected.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 50wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。  The obtained matrix resin was mixed with pulverized particles at a ratio of 50 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0030] 実施例 4 [0030] Example 4
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0031] 実施例 5 [0031] Example 5
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 20wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 20 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0032] 実施例 6 (1)粒子 [0032] Example 6 (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にしてマトリックス樹脂を得た。  A matrix resin was obtained in the same manner as in Example 2.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 5wt%の割合で配合し、混合したものを実施 例 1と同様に成形して、厚さ 15mmの板を得た。  The obtained matrix resin was mixed with pulverized particles at a ratio of 5 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0033] 実施例 7 [0033] Example 7
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 5mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 5 mm.
[0034] 実施例 8 [0034] Example 8
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 30mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 30 mm.
[0035] 実施例 9 [0035] Example 9
(1)粒子  (1) Particle
目開き 15mmの篩を通過し目開き 10mmの篩上に残った粒子を捕集した以外は、 実施例 1と同様にして、 10〜 15mmの粒子を製造した。  Particles having a size of 10 to 15 mm were produced in the same manner as in Example 1 except that particles passing through a sieve having a mesh size of 15 mm and remaining on the sieve having a mesh size of 10 mm were collected.
(2)マトリックス樹脂 実施例 2と同様にして、マトリックス樹脂を得た。 (2) Matrix resin In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0036] 実施例 10 Example 10
(1)粒子  (1) Particle
実施例 9と同様にして、 10〜； 15mmの粒子を製造した。  In the same manner as in Example 9, particles of 10 to 15 mm were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 30mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 30 mm.
[0037] 実施例 11 [0037] Example 11
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。さらに、この板の裏面に青色のゥ レタン塗料をスプレー塗装した。  The obtained matrix resin was blended with pulverized particles in a proportion of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm. In addition, a blue urethane paint was sprayed on the back of the plate.
[0038] 比較例 1 [0038] Comparative Example 1
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
ビュルエステル樹脂（スチレンモノマー 80%含有） 100重量部、メチルェチルケトン パーオキサイド 3重量部、およびナフテン酸コバルト 0. 3重量部配合した。すなわち、 主剤をエポキシではない反応性硬化樹脂とした。 (3)成形体 100 parts by weight of butyl ester resin (containing 80% styrene monomer), 3 parts by weight of methyl ethyl ketone peroxide, and 0.3 part by weight of cobalt naphthenate were blended. That is, the main component is a reactive curable resin that is not an epoxy. (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 50wt%の割合で配合し、混合したものを離 型処理したガラス型に注型し、 25°Cで 6時間、さらに 50°Cで 1時間加熱硬化して、厚 さ 15mmの板を得た。  The resulting matrix resin is blended with pulverized particles in a proportion of 50 wt%, and the mixture is cast into a release-molded glass mold and heated and cured at 25 ° C for 6 hours and further at 50 ° C for 1 hour. A plate with a thickness of 15 mm was obtained.
[0039] 比較例 2 [0039] Comparative Example 2
(1)粒子  (1) Particle
3mm長にカットされた PMMAペレットを使用した。すなわち、使用した PMMAぺ レットは熱可塑性樹脂である。  PMMA pellets cut to 3 mm length were used. That is, the PMMA pellet used is a thermoplastic resin.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に PMMAペレット (粒子）を 50wt%の割合で配合し、混 合したものを実施例 1と同様に成形して、厚さ 15mmの板を得た。  PMMA pellets (particles) were blended in a ratio of 50 wt% to the obtained matrix resin, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0040] 比較例 3 [0040] Comparative Example 3
(1)粒子  (1) Particle
3mm長にカットされた PMMAペレットを使用した。  PMMA pellets cut to 3 mm length were used.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にしてマトリックス樹脂を得た。  A matrix resin was obtained in the same manner as in Example 2.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に PMMAペレット (粒子）を 20wt%の割合で配合し、混 合したものを実施例 1と同様に成形して、厚さ 15mmの板を得た。  PMMA pellets (particles) were blended at a ratio of 20 wt% to the obtained matrix resin, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0041] 比較例 4 [0041] Comparative Example 4
(1)粒子  (1) Particle
目開き 0. 1mmの篩下に落下した粒子を捕集する以外は、実施例 1と同様にして、 0. 1mm以下の粒子を製造した。  Particles having a size of 0.1 mm or less were produced in the same manner as in Example 1 except that the particles dropped under the sieve having a mesh opening of 0.1 mm were collected.
(2)マトリックス樹脂  (2) Matrix resin
実施例 2と同様にして、マトリックス樹脂を得た。  In the same manner as in Example 2, a matrix resin was obtained.
(3)成形体 得られたマトリックス樹脂に粉砕粒子を 30wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。 (3) Molded body The obtained matrix resin was blended with pulverized particles at a ratio of 30 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0042] 比較例 5 [0042] Comparative Example 5
(1)粒子  (1) Particle
実施例 3と同様にして、 4〜6mmの粒子を製造した。  In the same manner as in Example 3, 4 to 6 mm particles were produced.
(2)マトリックス樹脂  (2) Matrix resin
ビスフエノール A型エポキシ樹脂 100重量部、メチルへキサヒドロ無水フタル酸 86 重量部、および硬化促進剤として 4級アンモニゥム塩 3重量部を混合した。すなわち 、前記粒子と全く組成の同じマトリックス樹脂を使用した。  100 parts by weight of bisphenol A type epoxy resin, 86 parts by weight of methylhexahydrophthalic anhydride, and 3 parts by weight of quaternary ammonium salt as a curing accelerator were mixed. That is, a matrix resin having the same composition as the particles was used.
(3)成形体  (3) Molded body
得られたマトリックス樹脂に粉砕粒子を 40wt%の割合で配合し、混合したものを実 施例 1と同様に成形して、厚さ 15mmの板を得た。  The obtained matrix resin was blended with pulverized particles at a ratio of 40 wt%, and the mixture was molded in the same manner as in Example 1 to obtain a plate having a thickness of 15 mm.
[0043] 評 ¼言式,験 成7 ネ斤 [0043] Review ¼ Testimony, Test 7
(1)分析  (1) Analysis
マトリックスと粒子とにおいて、組成の相違を以下の方法により調べた。成形体を厚 み方向に lmm厚さに切断してマトリックスと粒子を認識しやすくし、マトリックスから 0 . 5mgおよび粒子から 0. 5mgのサンプルをそれぞれ採取した。これを、熱分解 GC MSにより分析した。分析条件は表 1に示される通りとした。  The difference in composition between the matrix and the particles was examined by the following method. The molded body was cut to a thickness of 1 mm in the thickness direction to make it easy to recognize the matrix and particles. Samples of 0.5 mg from the matrix and 0.5 mg from the particles were taken, respectively. This was analyzed by pyrolysis GC MS. The analysis conditions were as shown in Table 1.
[0044] [表 1コ 熱分解 GC-MS [0044] [Table 1 Pyrolysis GC-MS
熱分解条件 .  Thermal decomposition conditions
装置名 PY-2020D (FRONTIER LAB)  Device name PY-2020D (FRONTIER LAB)
分^ &度 550 。C (0.5 min)  Minutes & degrees 550. C (0.5 min)
ィンター.フエ一ス温度 320 X, (AUTO)  Winter face temperature 320 X, (AUTO)
GC-MS条件  GC-MS conditions
装置名 5890SERIES Π /HP597IA (HEWLETT PACKERD)  Device name 5890SERIES Π / HP597IA (HEWLETT PACKERD)
カラム Capillaly Column I.D. 0.25 mmX 30 m  Column Capillaly Column I.D.0.25 mmX 30 m
liquid Pha se UA-5  liquid Pha se UA-5
Fflm Thickness 0.25 μ, τα  Fflm Thickness 0.25 μ, τα
キヤリァガス He :8.0 si  Carrier gas He: 8.0 si
スプリット比 1 / 50  Split ratio 1/50
温度 Injector 320。C  Temperature Injector 320. C
Column 40 °C (0 min)→20 °C/ min→320 °C(10 min) Column 40 ° C (0 min) → 20 ° C / min → 320 ° C (10 min)
Detector 280 °G Detector 280 ° G
MS Scan (mlz： 29-550) [0045] (2)結果 MS Scan (mlz: 29-550) [0045] (2) Results
実施例 1についての熱分解 GC— MSによる分析結果を、マトリックスについて図 2 に、粒子について図 3に示す。なお、縦軸は検出信号強度、横軸は保持時間を表し ており、図 2と図 3の横軸のスケールについてはピーク位置が比較しやすいようにそろ えている。  The results of pyrolysis GC-MS analysis for Example 1 are shown in Fig. 2 for the matrix and Fig. 3 for the particles. The vertical axis represents the detected signal intensity, and the horizontal axis represents the retention time. The scales on the horizontal axis in Figs. 2 and 3 are aligned so that the peak positions can be easily compared.
[0046] マトリックスの結果にはビスフエノール A型エポキシ樹脂由来のピークが現れ脂環式 エポキシ樹脂由来のピークは存在しない。一方、粒子の結果には脂環式エポキシ樹 脂のピークが現れ BPA型エポキシ樹脂由来のピークは存在しない。これらの結果は 、配合内容と一致しており、マトリックスと粒子の熱分解 GC— MS分析を行うことでそ の組成の違いを分析することができた。また、異なる組成として配合量を変えた場合 も、熱分解 GC— MSで得られたピークをマトリックスと粒子で比較することで、配合量 の違いがそれぞれに由来するピークの強度比として測定できる。  [0046] The matrix results show a peak derived from the bisphenol A type epoxy resin and no peak derived from the alicyclic epoxy resin. On the other hand, the alicyclic epoxy resin peak appears in the particle results, and there is no peak derived from the BPA type epoxy resin. These results are consistent with the contents of the formulation, and the compositional differences could be analyzed by pyrolysis GC-MS analysis of the matrix and particles. In addition, even when the compounding amount is changed as a different composition, by comparing the peaks obtained by pyrolysis GC-MS with the matrix and particles, the difference in the compounding amount can be measured as the intensity ratio of the peaks derived from each.
[0047] 評鍾,験 2量雷  [0047] Evaluation, Experiment 2
(1)耐熱性  (1) Heat resistance
成形体の上に 200°Cに熱した油の入った天ぶら鍋を 20分放置した後、成形体表 面の外観変化を以下の基準で評価した。  After leaving the pan with oil heated to 200 ° C for 20 minutes on the compact, the appearance change of the compact surface was evaluated according to the following criteria.
〇：変色、変形、光沢変化等の著しい変化が見られない。  ◯: Significant changes such as discoloration, deformation and gloss change are not observed.
X：著しい変化が見られる。  X: Significant changes are seen.
(2)透過率  (2) Transmittance
ASTMD1003に準拠して行った。すなわち、 haze-gard plus (BY gardner社製)を 使用し、成形体厚み方向の 550nmの光線を含む光源における全光線透過率を測 定した。このとき、塗装部を設けている場合はこの塗装部を切断あるいはサンディン グ等で削り落とし光沢仕上げとして測定した。また、厚みは 15mm以下とし、これ以上 の厚みの場合は同様に切断もしくは削り落として 15mm以下の厚みとし、光沢仕上 げとした後測定した。  This was performed according to ASTMD1003. That is, haze-gard plus (manufactured by BY gardner) was used to measure the total light transmittance in a light source including a 550 nm light beam in the thickness direction of the molded body. At this time, when a painted part was provided, the painted part was cut or sanded to measure the gloss finish. In addition, the thickness was 15 mm or less, and when the thickness was more than this, it was cut or scraped to a thickness of 15 mm or less, and the gloss finish was measured.
(3)柄鮮明性  (3) Pattern clarity
成形体を表面が上面にくるように平面的に置き、室内にて上部より目視にて外観を 観察し、以下の基準で評価を行った。 〇：粒子の輪郭が柄となって見える。 The molded body was placed in a plane so that the surface was on the upper surface, and the appearance was visually observed from above in the room, and evaluation was performed according to the following criteria. O: The outline of the particle appears as a pattern.
X：粒子の輪郭が柄となって見えにくい。  X: The particle outline is difficult to see due to the pattern.
[0048] (4)粒子径 [0048] (4) Particle size
粒子径は以下の通り測定した。すなわち、成形体を厚み方向に lmm程度に薄く切 断し、成形体の表面を基準線としたときのフェレット径（Feret径）を切断面にある 100 個の粒子につ!/、て計測し、単純平均を粒子径とした。  The particle size was measured as follows. That is, the compact is cut as thin as about 1 mm in the thickness direction, and the ferret diameter (Feret diameter) with the surface of the compact as the reference line is measured for 100 particles on the cut surface! The simple average was taken as the particle size.
[0049] (5)結果） [0049] (5) Results)
上記評価試験の結果は、表 2に示されるとおりであった。  The results of the evaluation test were as shown in Table 2.
[0050] [表 2] [0050] [Table 2]
Figure imgf000016_0001
Figure imgf000016_0001
[0051] 実施例;!〜 11の樹脂成形体は、 200°Cに熱せられた油の入った天ぷらなべを置い た場合にも著しい外観変化等は見られなかった。比較例 1は、耐熱性の低いポリエス テル樹脂配合物をマトリックスに使用すると、耐熱性の高いエポキシ樹脂配合物によ る粒子を配合してもマトリックスのポリエステル樹脂配合物が軟化し変形することによ り外観変化を起こすことを示してレ、る。  [0051] In the resin molded bodies of Examples;! To 11, no significant change in appearance was observed even when a tempura pan containing oil heated to 200 ° C was placed. In Comparative Example 1, when a polyester resin compound with low heat resistance is used in the matrix, the polyester resin compound in the matrix softens and deforms even when particles with an epoxy resin compound with high heat resistance are mixed. This indicates that the appearance will change more.
[0052] また、実施例 1〜； 11の樹脂成形体は、透明性や柄にも優れている。比較例 2は、マ トリックス樹脂がエポキシ樹脂配合物でも、配合粒子に耐熱性の低レ、アクリル粒子を 使用した場合、表面に露出したアクリル粒子自体が熱により変形し外観変化を引き起 こすを示している。また、エポキシ樹脂配合物は硬化時に発熱および硬化収縮が起 こるため、この影響と思われるアクリル粒子界面の白化が生じ、透明性や柄としても満 足のいくものが得られな力 た。さらに比較例 3の樹脂成形体は、粒子の配合量を 20 %に減らし、成形体表面近傍にアクリル粒子が存在せず、エポキシ樹脂配合物のマ トリックスのみの層を形成させたものである。この樹脂成形体の表面側にはマトリックス のみで形成された層があるため、耐熱性試験で外観変化は見られない。しかし、成 形時に生じるアクリル粒子界面の白化は同様に生じてしまい、柄鮮明性に劣るもので あった。 [0052] The resin molded bodies of Examples 1 to 11 are also excellent in transparency and pattern. In Comparative Example 2, even if the matrix resin is an epoxy resin compound, if acrylic particles with low heat resistance are used as the compounded particles, the acrylic particles exposed on the surface themselves are deformed by heat and cause a change in appearance. Indicates rubbing. In addition, since the epoxy resin composition generates heat and cure shrinkage during curing, whitening of the acrylic particle interface, which is thought to be due to this effect, occurred, and the transparency and handle were not satisfactory. Furthermore, the resin molded body of Comparative Example 3 was obtained by reducing the blending amount of the particles to 20%, forming no layer of acrylic particles in the vicinity of the surface of the molded body, and forming a matrix only of the epoxy resin blend. Since there is a layer formed only of the matrix on the surface side of the resin molded body, no change in appearance is observed in the heat resistance test. However, the whitening of the interface of the acrylic particles that occurred during the formation occurred in the same manner, and the pattern sharpness was inferior.
[0053] 実施例；!〜 3、および 9は、粒子径を変えると柄模様は変化する力 透明性や柄の 鮮明性は確保されて!/、ることを示して!/、る。実施例 3の成形体の写真を図 4として示 す。また、実施例 11の成形体の写真を図 5として、また比較例 4の成形体の写真を図 6として示す。両者を比較すると、比較例 4のように粒子が 0. 1mm以下の場合は、柄 として粒子の界面を視認できず、柄として機能しな力、つたことが分かる。  [0053] Examples:! To 3 and 9 show that the power of changing the pattern when the particle size is changed Transparency and the sharpness of the pattern are ensured! /. A photograph of the molded product of Example 3 is shown in FIG. A photograph of the molded product of Example 11 is shown in FIG. 5, and a photograph of the molded product of Comparative Example 4 is shown in FIG. Comparing the two, it can be seen that when the particle is 0.1 mm or less as in Comparative Example 4, the particle interface cannot be visually recognized as a handle, and the force does not function as a handle.
[0054] さらに、実施例 3〜6のように粒子配合量を変化させた場合、図 7および図 8のように 粒子層の厚みが変化していくことで柄模様が変化する。透明性や柄の鮮明性は確保 される。  [0054] Further, when the amount of particles is changed as in Examples 3 to 6, the pattern changes as the thickness of the particle layer changes as shown in Figs. Transparency and pattern clarity are ensured.
[0055] 粒子とマトリックスが全く同じ組成の比較例 5の樹脂成形体は、全光線透過率が 90 . 5%と透明性は高いが、粒子とマトリックス樹脂の屈折率差がほとんどなくなり、粒子 界面が非常に見えに《なり、柄の鮮明性は十分ではな力 た。  [0055] The resin molded body of Comparative Example 5 in which the particles and the matrix have exactly the same composition has high transparency with a total light transmittance of 90.5%, but there is almost no difference in the refractive index between the particles and the matrix resin. Became very visible, and the sharpness of the pattern was not sufficient.

Claims

請求の範囲 The scope of the claims
[1] マトリックスと、前記マトリックス中に分散された粒子とを含んでなる樹脂成形体であ つて、  [1] A resin molded body comprising a matrix and particles dispersed in the matrix,
前記マトリックスがエポキシ樹脂配合物からなり、  The matrix comprises an epoxy resin compound;
前記粒子が、前記マトリックスのエポキシ樹脂配合物とは異なる組成のエポキシ樹 脂配合物より構成されかつ前記樹脂成形体の表面を基準線としたフェレット径で lm m以上の大きさを有するものであることを特徴とする、樹脂成形体。  The particles are composed of an epoxy resin composition having a composition different from the epoxy resin composition of the matrix and have a ferret diameter of lm m or more with the surface of the resin molded body as a reference line. A resin molded body characterized by that.
[2] その裏面を着色した、請求項 1に記載の樹脂成形体。 [2] The resin molded product according to claim 1, wherein the back surface is colored.
[3] 前記マトリックスが無機粒子を実質的に含まない、請求項 1に記載の樹脂成形体。  [3] The resin molded article according to claim 1, wherein the matrix does not substantially contain inorganic particles.
[4] 前記エポキシ樹脂配合物が、エポキシ樹脂主剤と硬化剤とを含んでなり、前記ェポ キシ樹脂主剤が、芳香族系エポキシ樹脂または脂肪族系エポキシ樹脂である、請求 項 1に記載の樹脂成形体。 [4] The epoxy resin compound according to claim 1, wherein the epoxy resin composition includes an epoxy resin main component and a curing agent, and the epoxy resin main component is an aromatic epoxy resin or an aliphatic epoxy resin. Resin molded body.
[5] 前記粒子のエポキシ樹脂主剤または硬化剤を、マトリックスのそれとは異なるものを 用いるまたはその配合割合を変えることで、前記粒子が前記マトリックスのエポキシ樹 脂配合物とは異なる組成のエポキシ樹脂配合物とされた、請求項 4に記載の樹脂成 形体。 [5] The epoxy resin main component or curing agent of the particles is different from that of the matrix, or the blending ratio thereof is changed so that the particles have an epoxy resin composition different from that of the matrix epoxy resin compound. The resin molded product according to claim 4, which is a product.
[6] 請求項 1に記載の樹脂成形体を表面に有した、物品。  [6] An article having the resin molded body according to claim 1 on its surface.
[7] 流し、洗面台、キッチンカウンター、カウンター、テーブル、または浴槽である、請求 項 6に記載の物品。  [7] The article of claim 6, which is a sink, a sink, a kitchen counter, a counter, a table, or a bathtub.
PCT/JP2007/073500 2006-12-05 2007-12-05 Resin molded product with high level of surface design and article having the resin molded product on its surface WO2008069239A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1142177A (en) * 1997-07-28 1999-02-16 Build:Kk Bathtub having high warm water durability and repairing method therefor
JP2003171442A (en) * 2001-04-06 2003-06-20 Toto Ltd Resin molding composition, resin molded product and method for producing them
JP2003266434A (en) * 2002-03-14 2003-09-24 Toto Ltd Manufacturing method for resin molded body and manufacturing method for bulk mold compound for preparing resin molded body
JP2004269645A (en) * 2003-03-07 2004-09-30 Toto Ltd Resin molded article and method for producing the same
JP2006081823A (en) * 2004-09-17 2006-03-30 Virtual Net.Com:Kk Kitchen counter
JP2006257158A (en) * 2005-03-15 2006-09-28 Asahi Kasei Chemicals Corp Reinforced ptt(polytrimethylene terephthalate) resin composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1142177A (en) * 1997-07-28 1999-02-16 Build:Kk Bathtub having high warm water durability and repairing method therefor
JP2003171442A (en) * 2001-04-06 2003-06-20 Toto Ltd Resin molding composition, resin molded product and method for producing them
JP2003266434A (en) * 2002-03-14 2003-09-24 Toto Ltd Manufacturing method for resin molded body and manufacturing method for bulk mold compound for preparing resin molded body
JP2004269645A (en) * 2003-03-07 2004-09-30 Toto Ltd Resin molded article and method for producing the same
JP2006081823A (en) * 2004-09-17 2006-03-30 Virtual Net.Com:Kk Kitchen counter
JP2006257158A (en) * 2005-03-15 2006-09-28 Asahi Kasei Chemicals Corp Reinforced ptt(polytrimethylene terephthalate) resin composition

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