JP2017087527A - Method for manufacturing artificial marble - Google Patents
Method for manufacturing artificial marble Download PDFInfo
- Publication number
- JP2017087527A JP2017087527A JP2015219381A JP2015219381A JP2017087527A JP 2017087527 A JP2017087527 A JP 2017087527A JP 2015219381 A JP2015219381 A JP 2015219381A JP 2015219381 A JP2015219381 A JP 2015219381A JP 2017087527 A JP2017087527 A JP 2017087527A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- thermosetting resin
- mold
- pattern
- artificial marble
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000002928 artificial marble Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 146
- 239000011347 resin Substances 0.000 claims abstract description 146
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 238000000465 moulding Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 11
- 239000000945 filler Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000004579 marble Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000019646 color tone Nutrition 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000005080 phosphorescent agent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth salts Chemical class 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本発明は、人造大理石の製造方法に関する。 The present invention relates to a method for producing artificial marble.
流れ模様は大理石を特徴付ける意匠である。従来、人造大理石の意匠に高級感を付与することを目的として、流れ柄を有する人造大理石の製造方法に関する検討が行われてきた。 The flow pattern is a design that characterizes marble. Conventionally, for the purpose of imparting a high-class feeling to a design of an artificial marble, studies have been made on a method for manufacturing an artificial marble having a flowing pattern.
大理石模様を有する人造大理石の製造方法として、意匠を有するフィルムやゲルコート等と同時成形したり、あるいは成形後に塗装したりすることで、最表面のみに意匠を発現させる方法が知られている。しかし、これらの方法は、無垢材料を使用するものではないため、加工面や小口には大理石模様が存在せず、意匠面も使用時の磨耗劣化等により大理石模様が消失するおそれがある。このような問題を解消するためには、無垢材料を使用することが望ましい。 As a method for producing an artificial marble having a marble pattern, there is known a method in which a design is expressed only on the outermost surface by simultaneous molding with a film having a design, a gel coat or the like, or by coating after molding. However, since these methods do not use a solid material, there is no marble pattern on the processed surface or the edge, and there is a possibility that the marble pattern may disappear due to wear deterioration during use of the design surface. In order to solve such a problem, it is desirable to use a solid material.
人造大理石の製造方法として、密閉型のキャビティを有する金型内に、１つまたは複数の注入口より樹脂を注入して硬化させる注型成形工法が知られている（特許文献１、２）。また、開放状態のキャビティに樹脂を注入して硬化させるオープン注入工法や、ベルトコンベア等に樹脂を連続的に供給して硬化させる押出成形工法が知られている。 As a method for producing artificial marble, a casting molding method is known in which a resin is injected from one or a plurality of injection ports into a mold having a sealed cavity (Patent Documents 1 and 2). Also known are an open injection method in which resin is injected into an open cavity and cured, and an extrusion method in which resin is continuously supplied to a belt conveyor and cured.
無垢材料を使用した流れ柄を有する人造大理石の製造方法としては、オープン注入工法にて複数の色調の樹脂を使用して任意の模様を描く方法や、押出成形工法にてベース樹脂に差し込んだノズル等で色調の異なる柄用樹脂を供給する方法が知られている。 As a manufacturing method of artificial marble with a flowing pattern using solid materials, there are a method of drawing an arbitrary pattern using resins of multiple colors by the open injection method, and a nozzle inserted into the base resin by an extrusion method For example, a method of supplying a pattern resin having different color tones is known.
これらのうちオープン注入工法は、自由な模様を描画できるが、コストが高くなりやすいという問題や、模様を描く時に樹脂中の有機溶剤が揮発し続けて作業環境が劣悪となるという問題がある。 Among these, the open injection method can draw a free pattern, but has a problem that the cost tends to be high, and a problem that the organic solvent in the resin continues to evaporate when the pattern is drawn, resulting in a poor working environment.
また、押出成形工法には、樹脂の流れを利用した自然な模様が実現できるが、大規模な設備が必要となるという問題がある。 In addition, the extrusion molding method can realize a natural pattern using the flow of the resin, but has a problem that a large-scale facility is required.
注型成形工法は、密閉型のキャビティを使用するために、オープン注入工法で問題となる溶剤の揮発を抑制でき、押出成形工法と比較して設備も小規模となることから、上述の問題が生じにくい工法である。 Since the casting molding method uses a closed cavity, it can suppress the volatilization of the solvent, which is a problem with the open injection method, and the equipment becomes smaller than the extrusion molding method. It is a construction method that is unlikely to occur.
しかし、従来の注型成形工法では、大理石のような自然な流れ模様、すなわち巨大な岩より切り出したかのような均一な模様が得られないため、自然な流れ模様を有する人造大理石は、注型成形工法によっては製造が困難であった。 However, the conventional cast molding method cannot produce a natural flow pattern like marble, that is, a uniform pattern as if it was cut out of a huge rock. Depending on the construction method, it was difficult to manufacture.
本発明は、以上の通りの事情に鑑みてなされたものであり、注型成形工法によって、自然な模様の流れ柄を付与することができる人造大理石の製造方法を提供することを課題としている。 This invention is made | formed in view of the situation as mentioned above, and makes it the subject to provide the manufacturing method of the artificial marble which can provide the flow pattern of a natural pattern with the casting method.
上記の課題を解決するために、本発明の人造大理石の製造方法は、第１の熱硬化性樹脂と、この第１の熱硬化性樹脂に比べて色調が異なり粘度が高い第２の熱硬化性樹脂とを、第２の熱硬化性樹脂が筋状となるように混合し、得られた混合樹脂を金型の注入口から金型内に供給して、混合樹脂を硬化させる、流れ柄を有する人造大理石の製造方法であって、第２の熱硬化性樹脂に直鎖状高分子を添加し、前記混合樹脂を前記金型の注入口から前記金型内に供給する際における、前記第２の熱硬化性樹脂の正接損失ｔａｎδを０．２〜９０とすることを特徴としている。 In order to solve the above-described problems, the method for producing an artificial marble according to the present invention includes a first thermosetting resin and a second thermosetting resin having a different color tone and a higher viscosity than the first thermosetting resin. The mixed resin is mixed with the second thermosetting resin so that the second thermosetting resin has a streak shape, and the obtained mixed resin is supplied into the mold from the injection port of the mold to cure the mixed resin. A method for producing an artificial marble, comprising: adding a linear polymer to a second thermosetting resin, and supplying the mixed resin from the injection port of the mold into the mold. The tangent loss tan δ of the second thermosetting resin is set to 0.2 to 90.
本発明によれば、注型成形工法によって、自然な模様の流れ柄を付与することができる。 According to the present invention, a natural pattern flow pattern can be imparted by a casting method.
以下に、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
本実施形態の人造大理石の製造方法は、流れ柄を有する人造大理石の製造方法であって、第１の熱硬化性樹脂と、この第１の熱硬化性樹脂に比べて色調が異なり粘度が高い第２の熱硬化性樹脂とが、第２の熱硬化性樹脂が筋状となるように混合される。得られた混合樹脂は、金型の注入口から金型内に供給され、混合樹脂が硬化される。そして本実施形態の人造大理石の製造方法は、第２の熱硬化性樹脂に直鎖状高分子を添加し、前記混合樹脂を前記金型の注入口から前記金型内に供給する際における、前記第２の熱硬化性樹脂の正接損失ｔａｎδを０．２〜９０とすることを特徴としている。 The method for producing an artificial marble according to the present embodiment is a method for producing an artificial marble having a flowing pattern, and has a different color tone and a higher viscosity than the first thermosetting resin and the first thermosetting resin. The second thermosetting resin is mixed so that the second thermosetting resin has a streak shape. The obtained mixed resin is supplied into the mold from the injection port of the mold, and the mixed resin is cured. And the manufacturing method of the artificial marble of this embodiment adds a linear polymer to the second thermosetting resin, and supplies the mixed resin from the injection port of the mold into the mold. The tangent loss tan δ of the second thermosetting resin is 0.2 to 90.
本実施形態で使用される第１の熱硬化性樹脂は、硬化することによって成形品の基調となるベース樹脂である。第２の熱硬化性樹脂は、硬化することによってベース樹脂の基調に流れ柄を付与する柄用樹脂である。 The first thermosetting resin used in the present embodiment is a base resin that becomes the basis of a molded product by being cured. The second thermosetting resin is a pattern resin that imparts a flowing pattern to the base tone of the base resin by curing.
第１および第２の熱硬化性樹脂としては、例えば、主成分である樹脂に、充填剤、硬化剤等の添加剤を適宜配合した樹脂組成物を用いることができる。 As the first and second thermosetting resins, for example, a resin composition in which additives such as a filler and a curing agent are appropriately blended with a resin as a main component can be used.
樹脂としては、例えば、ビニルエステル樹脂、不飽和ポリエステル樹脂、アクリル樹脂、エポキシ樹脂等が挙げられる。これらは１種単独で使用してもよく、２種以上を併用してもよい。 Examples of the resin include vinyl ester resin, unsaturated polyester resin, acrylic resin, and epoxy resin. These may be used alone or in combination of two or more.
充填剤としては、例えば、水酸化アルミニウム、炭酸カルシウム、シリカ、ガラスパウダー等が挙げられる。これらは１種単独で使用してもよく、２種以上を併用してもよい。 Examples of the filler include aluminum hydroxide, calcium carbonate, silica, and glass powder. These may be used alone or in combination of two or more.
充填剤の配合量は、目的とする粘度等の特性などにもよるが、例えば、熱硬化性樹脂１００質量部に対して１００〜３００質量部である。充填剤の配合量がこの範囲であると、成形品の耐衝撃強度、耐熱性を確保することができる。充填剤の粒径は、小さいほど人造大理石の耐衝撃強度を向上することができるが、熱硬化性樹脂の粘度を急激に上昇させて製造が困難となる場合があるため配合量を考慮して適宜設定することが望ましい。 The blending amount of the filler is, for example, 100 to 300 parts by mass with respect to 100 parts by mass of the thermosetting resin, although it depends on characteristics such as the target viscosity. When the blending amount of the filler is within this range, the impact resistance strength and heat resistance of the molded product can be ensured. As the particle size of the filler is smaller, the impact strength of the artificial marble can be improved, but the viscosity of the thermosetting resin may be increased rapidly, which may make it difficult to manufacture. It is desirable to set appropriately.
硬化剤は、人造大理石を成形する際の温度によって、半減期温度から選定することができる。具体的には、例えば、有機過酸化物を用いることができ、有機過酸化物として、例えば、１,１,３,３−テトラメチルブチルパーオキシ２−エチルヘキサノエート、ｔ−ヘキシルパーオキシ２−エチルヘキサノエート等が挙げられる。 The curing agent can be selected from the half-life temperature depending on the temperature at which the artificial marble is molded. Specifically, for example, an organic peroxide can be used. Examples of the organic peroxide include 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate etc. are mentioned.
第１および第２の熱硬化性樹脂には、上記以外の添加剤として、例えば、着色剤、紫外線吸収剤、減粘剤、離型剤、ガラス繊維等を配合することができる。各種着色剤（トナー）を配合することで、所望の色調に着色された、色調の異なる樹脂組成物を形成することができる。また、より高い意匠性を表現するために、蓄光剤や蛍光剤を配合することもできる。 In the first and second thermosetting resins, for example, a colorant, an ultraviolet absorber, a viscosity reducing agent, a release agent, glass fiber, and the like can be blended as additives other than those described above. By blending various colorants (toners), it is possible to form resin compositions with different color tones that are colored in a desired color tone. Moreover, in order to express higher designability, a phosphorescent agent and a fluorescent agent can also be mix | blended.
また、第１および第２の熱硬化性樹脂は、例えば２０〜５０Ｔｏｒｒ程度の減圧下で真空脱泡の処理をすることができる。このようにして脱泡処理された色調の異なる第１および第２の熱硬化性樹脂の各々を個別に減圧状態から開放した後、これらを混合することができる。 The first and second thermosetting resins can be subjected to vacuum defoaming treatment under a reduced pressure of, for example, about 20 to 50 Torr. Each of the first and second thermosetting resins having different color tones subjected to the defoaming treatment as described above can be individually released from the reduced pressure state and then mixed.
柄用樹脂である第２の熱硬化性樹脂は、第１の熱硬化性樹脂に比べて粘度が高いものである。第２の熱硬化性樹脂の粘度は、直鎖状高分子等の高分子成分を高濃度化または高分子量化することで高粘度化したり、充填剤を増量したり、充填剤を微粒子化させたりすることで調整できる。また、微細粒子（アエロジル（登録商標）等）を添加することでも調整できる。酸基を有する不飽和ポリエステル樹脂を使用する場合や、ビニルエステル樹脂やアクリル樹脂のうち特定のものを使用する場合には、増粘剤として希土類塩（酸化マグネシウム等）を使用することで粘度を調整できる。またヒドロキシル基を有する不飽和ポリエステル樹脂、ヒドロキシル基を有するビニルエステル樹脂、ヒドロキシル基を有するアクリル樹脂には、増粘剤としてイソシアネートを使用することで粘度を調整できる。アクリル樹脂の場合、反応重合度が異なる樹脂を使用することでも粘度を調整できる。 The second thermosetting resin, which is a pattern resin, has a higher viscosity than the first thermosetting resin. The viscosity of the second thermosetting resin can be increased by increasing the concentration or increasing the molecular weight of a polymer component such as a linear polymer, increasing the amount of filler, or making the filler finer. Can be adjusted. It can also be adjusted by adding fine particles (such as Aerosil (registered trademark)). When using unsaturated polyester resins with acid groups, or when using certain vinyl ester resins or acrylic resins, the viscosity can be increased by using rare earth salts (magnesium oxide, etc.) as thickeners. Can be adjusted. Moreover, the viscosity can be adjusted by using isocyanate as a thickener for unsaturated polyester resins having hydroxyl groups, vinyl ester resins having hydroxyl groups, and acrylic resins having hydroxyl groups. In the case of an acrylic resin, the viscosity can be adjusted by using resins having different reaction polymerization degrees.
第２の熱硬化性樹脂の粘度は、第１の熱硬化性樹脂の粘度に比べて１．５倍以上とすることが好ましい。 The viscosity of the second thermosetting resin is preferably 1.5 times or more than the viscosity of the first thermosetting resin.
本実施形態の人造大理石の製造方法では、第２の熱硬化性樹脂に直鎖状高分子を添加する。これにより、第２の熱硬化性樹脂の粘度および正接損失を調整し、自然な模様の流れ柄を付与することができる。 In the method for producing artificial marble according to this embodiment, a linear polymer is added to the second thermosetting resin. Thereby, the viscosity and tangent loss of the second thermosetting resin can be adjusted, and a natural pattern flow pattern can be imparted.
ここで直鎖状高分子は、モノマー単位が重合した繰り返し単位からなる直鎖構造を有し、かつ、モノマー単位が重合した繰り返し単位による分岐鎖を持たないものである。繰り返し単位の結合の例としては、オレフィン由来の飽和炭素結合、エステル結合、エーテル結合などが挙げられる。この直鎖状高分子は、混合樹脂を金型内で硬化後にマトリックスとなる樹脂ポリマーと同一である必要はない。 Here, the linear polymer has a linear structure composed of repeating units obtained by polymerizing monomer units, and does not have a branched chain formed by repeating units obtained by polymerizing monomer units. Examples of the bond of the repeating unit include a saturated carbon bond derived from an olefin, an ester bond, an ether bond and the like. This linear polymer need not be the same as the resin polymer that becomes the matrix after curing the mixed resin in the mold.
直鎖状高分子としては、アクリル系高分子が挙げられる。直鎖状高分子がアクリル系高分子であると、第２の熱硬化性樹脂の正接損失を調整し、自然な模様の流れ柄を付与するのに適している。 Examples of the linear polymer include acrylic polymers. When the linear polymer is an acrylic polymer, it is suitable for adjusting the tangent loss of the second thermosetting resin and giving a natural pattern flow pattern.
アクリル系高分子としては、ポリメチルメタクリレートや、アクリル系のコポリマー等が挙げられる。 Examples of the acrylic polymer include polymethyl methacrylate and an acrylic copolymer.
直鎖状高分子としては、高粘度で混合が困難な場合、パウダー状の直鎖状高分子を好ましく用いることができる。このパウダー状の直鎖状高分子は、第２の熱硬化性樹脂の各成分を均一混合する段階から入っている必要はなく、パウダー状の直鎖状高分子以外の各成分を均一混合したものを調製後に後添加してもよい。第２の熱硬化性樹脂の各成分を均一混合する段階から直鎖状高分子を添加すると第２の熱硬化性樹脂の粘度が高くなるため混合が困難となる場合も懸念されるが、パウダー状の直鎖状高分子を後添加すれば、混合時は柔らかく、放置後パウダーが溶けた際に適度に混ざった状態となる。 As the linear polymer, a powdery linear polymer can be preferably used when mixing is difficult due to high viscosity. This powder-like linear polymer does not need to be included from the stage of uniformly mixing each component of the second thermosetting resin, and each component other than the powder-like linear polymer is uniformly mixed. Things may be added later after preparation. If the linear polymer is added from the stage of uniformly mixing the components of the second thermosetting resin, the viscosity of the second thermosetting resin increases, and there is concern that mixing may be difficult. If a linear polymer is added later, it will be soft when mixed, and will be properly mixed when the powder melts after standing.
パウダー状の直鎖状高分子としては、ポリメチルメタクリレート（三菱レイヨン製ダイヤナールシリーズ）等が挙げられる。 Examples of the powdery linear polymer include polymethyl methacrylate (Mitsubishi Rayon's Dianal series).
本実施形態の人造大理石の製造方法では、第２の熱硬化性樹脂に直鎖状高分子を添加することによって、粘度と正接損失が調整される。 In the method for producing artificial marble according to this embodiment, the viscosity and tangent loss are adjusted by adding a linear polymer to the second thermosetting resin.
混合樹脂を金型の注入口から金型内に供給する際における第２の熱硬化性樹脂の粘度ηは、１０〜５×１０５Ｐａ・ｓとすることが好ましく、５００〜５×１０４Ｐａ・ｓとすることがより好ましい。 The viscosity η of the second thermosetting resin when the mixed resin is supplied into the mold from the mold inlet is preferably 10 to 5 × 10 5 Pa · s, and 500 to 5 × 10 4. More preferably, it is Pa · s.
混合樹脂を金型の注入口から金型内に供給する際における第２の熱硬化性樹脂の正接損失ｔａｎδは、０．２〜９０とする。この範囲内にすると、ややぼやけた大理石柄である、自然な模様の流れ柄を実現することができる。 The tangent loss tan δ of the second thermosetting resin when the mixed resin is supplied from the mold inlet into the mold is 0.2 to 90. Within this range, a natural pattern flow pattern, which is a slightly blurred marble pattern, can be realized.
注型成形工法に使用する材料は、多くの場合粘度ηのみで評価されてきた。しかし、物質の「動きやすさ」を表すパラメータは粘度だけではない。本発明者は検討の結果、混合する際の第２の熱硬化性樹脂については、「粘度」だけでなく「弾性」についても考慮する必要があることを見出した。 In many cases, the material used for the casting method has been evaluated only with the viscosity η. However, viscosity is not the only parameter that represents the “movability” of a substance. As a result of the study, the present inventor has found that it is necessary to consider not only “viscosity” but also “elasticity” for the second thermosetting resin at the time of mixing.
流体の弾性を表すパラメータに、正接損失ｔａｎδがある。ｔａｎδが小さいほど弾性体的（ねばっこい）であり、大きいと粘性体的（さらさら）である。 There is a tangent loss tan δ as a parameter representing the elasticity of the fluid. Smaller tan δ is more elastic (sticky) and larger is more viscous (smooth).
自然な大理石柄を実現するためには、第２の熱硬化性樹脂が適度に伸びて、溶ける必要がある。そのためには、実際の成形条件に応じた温度と流速において測定を行った第２の熱硬化性樹脂の粘度および正接損失を、一定の範囲内に保つ必要がある。 In order to realize a natural marble pattern, the second thermosetting resin needs to be appropriately stretched and melted. For this purpose, it is necessary to keep the viscosity and tangent loss of the second thermosetting resin measured at a temperature and a flow rate according to actual molding conditions within a certain range.
第２の熱硬化性樹脂の正接損失と粘度を制御するためには、使用する樹脂ポリマーの分子構造を制御する必要がある。 In order to control the tangent loss and viscosity of the second thermosetting resin, it is necessary to control the molecular structure of the resin polymer used.
柄用樹脂として使用される熱硬化性樹脂は一般に、分子量１０００＜Ｍｗ＜５００００程度の樹脂ポリマーと、樹脂ポリマーを希釈するスチレン等の重合性モノマー、そして充填剤、硬化剤等の様々な添加剤を混合して作製される。 The thermosetting resin used as a pattern resin is generally a resin polymer having a molecular weight of 1000 <Mw <50000, a polymerizable monomer such as styrene for diluting the resin polymer, and various additives such as a filler and a curing agent. It is made by mixing.
この柄用樹脂コンパウンドの粘度および正接損失は、それぞれの構成要素の配合比と、樹脂ポリマーの分子構造によって決定される。全体に占めるモノマーの比率が高いと低粘度、高正接損失となり、充填剤と樹脂ポリマーの比率が高いと高粘度、低正接損失となる。 The viscosity and tangent loss of the pattern resin compound are determined by the blending ratio of each component and the molecular structure of the resin polymer. When the ratio of the monomer to the whole is high, the viscosity and the tangent loss are low, and when the ratio of the filler and the resin polymer is high, the viscosity and the tangent loss are high.
粘度および正接損失を大きく変化させるためには、樹脂ポリマーの分子構造を検討する必要がある。Ｚ平均分子量Ｍｚが樹脂粘度とフィットする指数として用いられることからもわかるように、樹脂材料の流動性を制御するのはポリマー中の高分子成分である。この高分子成分が直鎖であればコンパウンドは高正接損失となり、分岐鎖をもつと低正接損失となる。したがって本実施形態では、第２の熱硬化性樹脂に直鎖状高分子を添加している。これにより、第２の熱硬化性樹脂の粘度および正接損失を調整し、自然な模様の流れ柄を付与することができる。 In order to greatly change the viscosity and tangent loss, it is necessary to study the molecular structure of the resin polymer. As can be seen from the fact that the Z average molecular weight Mz is used as an index that fits the resin viscosity, it is the polymer component in the polymer that controls the fluidity of the resin material. If the polymer component is a straight chain, the compound has a high tangent loss, and if it has a branched chain, the compound has a low tangent loss. Therefore, in this embodiment, a linear polymer is added to the second thermosetting resin. Thereby, the viscosity and tangent loss of the second thermosetting resin can be adjusted, and a natural pattern flow pattern can be imparted.
本実施形態の人造大理石の製造方法では、第１の熱硬化性樹脂と第２の熱硬化性樹脂とを、第２の熱硬化性樹脂が細い筋状となるように混合し、混合樹脂を調製する。例えば、第１の熱硬化性樹脂が入った注型タンクに、第２の熱硬化性樹脂を、シリンジ等を使用して線状に投入した後、適宜混合し、攪拌することで柄用樹脂である第２の熱硬化性樹脂を均一に分散させつつ、筋状となるように混合することができる。 In the method of manufacturing the artificial marble according to the present embodiment, the first thermosetting resin and the second thermosetting resin are mixed so that the second thermosetting resin has a fine streak shape, and the mixed resin is mixed. Prepare. For example, after the second thermosetting resin is linearly introduced into a casting tank containing the first thermosetting resin using a syringe or the like, the pattern resin is appropriately mixed and stirred. The second thermosetting resin can be mixed so as to form a streak while being uniformly dispersed.
第２の熱硬化性樹脂の第１の熱硬化性樹脂に対する混合比は、第１の熱硬化性樹脂を１とした場合、質量比で０．００１〜０．８とすることが好ましく、意匠性を考慮すると０．０１〜０．５とすることがより好ましい。 The mixing ratio of the second thermosetting resin to the first thermosetting resin is preferably 0.001 to 0.8 in terms of mass ratio when the first thermosetting resin is 1. In view of the properties, it is more preferably 0.01 to 0.5.
このようにして得られた混合樹脂は、金型の注入口から金型内に供給される。金型としては、一例として、図１に示すものを用いることができる。図１の例では、混合樹脂は、金型１の注入口２から金型１内に供給される。金型１内には、整流部材１０が設置されている。整流部材１０は、金型１内を上流側部分３と下流側部分４とに仕切り、かつ、注入口２から供給された混合樹脂の流路を複数に分割する。 The mixed resin thus obtained is supplied into the mold from the mold inlet. As an example of the mold, one shown in FIG. 1 can be used. In the example of FIG. 1, the mixed resin is supplied into the mold 1 from the inlet 2 of the mold 1. A rectifying member 10 is installed in the mold 1. The rectifying member 10 partitions the inside of the mold 1 into an upstream portion 3 and a downstream portion 4 and divides the mixed resin flow path supplied from the inlet 2 into a plurality of portions.
整流部材１０は、混合樹脂を通さない閉鎖部１１と、混合樹脂の流動が可能な開口部１２を交互に形成する。例えば、独立した複数の整流部材１０を一直線上に配置することで、閉鎖部１１と開口部１２を交互に形成し、かつ、金型１内を上流側部分３と下流側部分４とに仕切ることができる。あるいは、複数の閉鎖部１１と複数の開口部１２を連結して構成された一体の整流部材１０を用いて、金型１内を上流側部分３と下流側部分４とに仕切ることができる。 The rectifying member 10 alternately forms closed portions 11 that do not allow the mixed resin to pass therethrough and openings 12 that allow the mixed resin to flow. For example, by arranging a plurality of independent rectifying members 10 on a straight line, the closed portions 11 and the openings 12 are alternately formed, and the inside of the mold 1 is divided into the upstream portion 3 and the downstream portion 4. be able to. Or the inside of the metal mold | die 1 can be divided into the upstream part 3 and the downstream part 4 using the integral rectification | straightening member 10 comprised by connecting the some closure part 11 and the some opening part 12. FIG.
混合樹脂は、注入口２よりまず上流側部分３に供給された後、整流部材１０の開口部１２を通過することで流路が複数に分割される。これにより混合樹脂の流れは整流され、図１の符号２０の矢印として混合樹脂の流れを示すように金型１の注入口２とは反対側の端部に向かって、金型１の壁面と平行に直線状に流れる。 The mixed resin is first supplied to the upstream portion 3 from the injection port 2, and then passes through the opening 12 of the rectifying member 10, so that the flow path is divided into a plurality of parts. Thereby, the flow of the mixed resin is rectified, and the wall surface of the mold 1 is directed toward the end opposite to the injection port 2 of the mold 1 so as to indicate the flow of the mixed resin as an arrow 20 in FIG. It flows in a straight line parallel.
このようにして金型に混合樹脂を流し込んで供給した後、混合樹脂を硬化させて成形する。硬化の条件は、第１および第２の熱硬化性樹脂の種類、特性に応じて適宜設定することができるが、例えば、金型を常温または、１２０℃までの温度で加熱して、３０〜１２０分間静置することで硬化させる方法等が例示される。混合樹脂の硬化後は、金型を開いて、流れ柄が形成された人造大理石を取り出すことができる。 After the mixed resin is poured into the mold and supplied in this way, the mixed resin is cured and molded. The curing conditions can be appropriately set according to the types and characteristics of the first and second thermosetting resins. For example, the mold is heated at room temperature or a temperature up to 120 ° C. Examples include a method of curing by standing for 120 minutes. After the mixed resin is cured, the mold can be opened and the artificial marble with the flow pattern formed can be taken out.
本実施形態により製造された人造大理石は、自然な模様の流れ柄を有することから、意匠性、デザイン性に優れ、商品価値が高い。このような人造大理石の成形品は、例えば、洗面カウンター、キッチンカウンター等のカウンター材、あるいは浴槽、テーブル材、床材、壁面材等に好適に使用することができる。 The artificial marble manufactured according to the present embodiment has a natural pattern flow pattern, and thus has excellent design and design properties and high commercial value. Such a molded article of artificial marble can be suitably used, for example, as a counter material such as a wash counter or a kitchen counter, or a bathtub, a table material, a floor material, a wall surface material, or the like.
以上に説明した本実施形態の人造大理石の製造方法によれば、注型成形工法によって、
自然な模様の流れ柄を付与することができる。
According to the manufacturing method of the artificial marble of the present embodiment described above, by the cast molding method,
A natural flowing pattern can be added.
以下に、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。
１．配合
表１に示す配合に基づき、第１の熱硬化性樹脂（ベース樹脂）および第２の熱硬化性樹脂（柄用樹脂）を調製した。
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
1. Formulation Based on the formulation shown in Table 1, a first thermosetting resin (base resin) and a second thermosetting resin (pattern resin) were prepared.
ビニルエステル樹脂１００質量部、水酸化アルミニウム２００質量部、硬化剤１質量部、着色剤として白トナー０．６質量部、離型剤０．３質量部を配合し、第１の熱硬化性樹脂を調製した。 100 parts by weight of vinyl ester resin, 200 parts by weight of aluminum hydroxide, 1 part by weight of a curing agent, 0.6 part by weight of white toner as a colorant, and 0.3 part by weight of a release agent are blended to form a first thermosetting resin. Was prepared.
表１に示す配合で、樹脂、充填剤、添加剤を配合し、その他、硬化剤１質量部、着色剤黒トナー０．５質量部、離型剤０．３質量部を共通して添加した。混合後、常温にて２４時間静置したものを第２の熱硬化性樹脂として使用した。
２．注型準備
第１の熱硬化性樹脂が入った注型タンクに、第１の熱硬化性樹脂の０．５質量％の第２の熱硬化性樹脂を、シリンジを使用して線状に投入し、適宜に混合、攪拌することで第２の熱硬化性樹脂を均一に分散させた。これにより、第２の熱硬化性樹脂が筋状となるように混合された混合樹脂を得た。
３．注型
金型として、平面視で矩形状の上型および下型を備え、１つの注入口をこの矩形面の端部近傍に有するものを用意した。ホースを通じて注型タンクと金型の注入口を接続し、注型タンクに圧力をかけ、金型の注入口から金型内に混合樹脂を供給した。
４．成形
金型内に供給した混合樹脂を、９０℃で１時間加熱して硬化させた。
In the formulation shown in Table 1, a resin, a filler, and an additive were added, and in addition, 1 part by weight of a curing agent, 0.5 part by weight of a colorant black toner, and 0.3 part by weight of a release agent were added in common. . After mixing, the one that was allowed to stand at room temperature for 24 hours was used as the second thermosetting resin.
2. Casting preparation A casting tank containing the first thermosetting resin is charged with 0.5% by mass of the second thermosetting resin of the first thermosetting resin in a linear form using a syringe. And the 2nd thermosetting resin was disperse | distributed uniformly by mixing and stirring suitably. As a result, a mixed resin was obtained in which the second thermosetting resin was mixed so as to have a streak shape.
3. Casting molds were prepared that had a rectangular upper mold and a lower mold in plan view and had one inlet near the end of the rectangular surface. The casting tank and the mold inlet were connected through a hose, pressure was applied to the casting tank, and the mixed resin was supplied into the mold from the mold inlet.
4). The mixed resin supplied into the molding die was heated at 90 ° C. for 1 hour to be cured.
混合樹脂を金型内に供給し、硬化させて得られた人造大理石の平面写真を図２（ａ）〜（ｉ）に示す。
［測定および評価］
（第２の熱硬化性樹脂の粘度および正接損失）
第２の熱硬化性樹脂の粘度および正接損失は、トルクレオメーターを用いて測定した。
（意匠評価）
人造大理石の柄の状態より、ややぼやけた大理石柄が得られたものを○、第２の熱硬化性樹脂が溶解し、または途切れ、あるいは流れなかったものを×として評価した。
FIGS. 2A to 2I show planar photographs of the artificial marble obtained by supplying the mixed resin into the mold and curing it.
[Measurement and evaluation]
(Viscosity and tangent loss of the second thermosetting resin)
The viscosity and tangent loss of the second thermosetting resin were measured using a torque rheometer.
(Design evaluation)
From the state of the artificial marble pattern, the case where a slightly blurred marble pattern was obtained was evaluated as ◯, and the case where the second thermosetting resin was dissolved, interrupted or did not flow was evaluated as X.
上記の測定および評価の結果を表１に示す。 The results of the above measurement and evaluation are shown in Table 1.
＊１：ビニルエステル樹脂（固形分５０質量％、粘度約３００ｍＰａ・ｓ）
＊２：ビニルエステル樹脂（固形分７５質量％、粘度約１０Ｐａ・ｓ）
＊３：ＵＰ樹脂（固形分６０質量％、粘度８００ｍＰａ・ｓ）
＊４：水酸化アルミニウム（表面処理済）
＊５：アクリルパウダー（三菱レイヨンダイヤナールＬＰ３２０２）
＊６：酸化マグネシウム（協和化学＃４０）
図２（ａ）、（ｂ）より、実施例１、２は、ややぼやけた大理石柄であり、自然な模様の流れ柄を得ることができた。
* 1 : Vinyl ester resin (solid content 50% by mass, viscosity about 300 mPa · s)
* 2 : Vinyl ester resin (solid content: 75% by mass, viscosity: about 10 Pa · s)
* 3 : UP resin (solid content 60% by mass, viscosity 800 mPa · s)
* 4 : Aluminum hydroxide (surface treated)
* 5 : Acrylic powder (Mitsubishi Rayon Dianal LP3202)
* 6 : Magnesium oxide (Kyowa Chemical # 40)
2 (a) and 2 (b), Examples 1 and 2 were slightly blurred marble patterns, and a natural pattern flow pattern could be obtained.
比較例１は、直鎖状高分子を添加しなかった。正接損失が小さく、粘度も小さくなり、図２（ｃ）より、第２の熱硬化性樹脂が溶けて消失した。 In Comparative Example 1, no linear polymer was added. The tangent loss is small and the viscosity is small, and the second thermosetting resin melts and disappears from FIG.
比較例２は、直鎖状高分子を添加しなかった。正接損失が小さくなり、図２（ｄ）より、途切れが発生した。 In Comparative Example 2, no linear polymer was added. The tangent loss was reduced, and discontinuity occurred as shown in FIG.
比較例３は、直鎖状高分子を添加しなかった。正接損失が小さくなり、図２（ｅ）より、途切れが発生した。 In Comparative Example 3, no linear polymer was added. The tangent loss was reduced, and discontinuity occurred as shown in FIG.
比較例４は、直鎖状高分子を添加したが、粘度が小さくかつ正接損失が大きくなり、図２（ｆ）より、柄材が溶けて消失した。 In Comparative Example 4, a linear polymer was added, but the viscosity was small and the tangent loss was large, and the pattern material melted and disappeared from FIG.
比較例５は、直鎖状高分子を添加したが、正接損失が小さく、図２（ｇ）より、途切れが発生した。 In Comparative Example 5, a linear polymer was added, but the tangent loss was small, and discontinuity occurred from FIG.
比較例６は、直鎖状高分子を添加したが、正接損失が小さく、図２（ｈ）より、柄材が流れずそのまま残った。 In Comparative Example 6, a linear polymer was added, but the tangent loss was small, and the pattern material did not flow as shown in FIG.
比較例７は、増粘剤を添加したが、正接損失が小さくなり、図２（ｉ）より、柄材が流れずそのまま残った。 In Comparative Example 7, the thickener was added, but the tangent loss was reduced, and the pattern material did not flow as shown in FIG.
１ 金型
２ 注入口
1 Mold 2 Inlet
Claims (2)
前記第２の熱硬化性樹脂に直鎖状高分子を添加し、前記混合樹脂を前記金型の注入口から前記金型内に供給する際における、前記第２の熱硬化性樹脂の正接損失ｔａｎδを０．２〜９０とすることを特徴とする人造大理石の製造方法。 The first thermosetting resin and the second thermosetting resin having a different color tone and higher viscosity than the first thermosetting resin so that the second thermosetting resin has a streak shape. And mixing the obtained mixed resin into the mold through a mold inlet, and curing the mixed resin, a method for producing an artificial marble having a flow pattern,
Tangent loss of the second thermosetting resin when a linear polymer is added to the second thermosetting resin and the mixed resin is supplied into the mold from the injection port of the mold A method for producing artificial marble, wherein tan δ is 0.2 to 90.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015219381A JP2017087527A (en) | 2015-11-09 | 2015-11-09 | Method for manufacturing artificial marble |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015219381A JP2017087527A (en) | 2015-11-09 | 2015-11-09 | Method for manufacturing artificial marble |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2017087527A true JP2017087527A (en) | 2017-05-25 |
Family
ID=58769849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015219381A Pending JP2017087527A (en) | 2015-11-09 | 2015-11-09 | Method for manufacturing artificial marble |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2017087527A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02157146A (en) * | 1988-12-09 | 1990-06-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of artificial stone fitted with pattern |
| JPH08174570A (en) * | 1994-12-21 | 1996-07-09 | Matsushita Electric Works Ltd | Patterning method of scagliola |
| JP2001114546A (en) * | 1999-10-15 | 2001-04-24 | Matsushita Electric Works Ltd | Method for producing artificial marble |
| WO2001098429A1 (en) * | 2000-06-22 | 2001-12-27 | Mitsubishi Rayon Co., Ltd. | Thickening agent, thickening composition and process for producing the same, sheet molding compound or bulk molding compound and process for producing the same, and molded resin and process for producing the same |
| KR20030044249A (en) * | 2001-11-29 | 2003-06-09 | 제일모직주식회사 | Method of Manufacturing Artificial Marble Having Inlay Pattern |
| JP2004263135A (en) * | 2003-03-04 | 2004-09-24 | Mitsubishi Rayon Co Ltd | (meth)acrylic resin composition, molded resin article and method for producing molded resin article |
| JP2008524020A (en) * | 2004-12-17 | 2008-07-10 | チェイル インダストリーズ インコーポレイテッド | Artificial marble having crack pattern and manufacturing method thereof |
| JP2016198889A (en) * | 2015-04-07 | 2016-12-01 | パナソニックＩｐマネジメント株式会社 | Method for producing artificial marble |
-
2015
- 2015-11-09 JP JP2015219381A patent/JP2017087527A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02157146A (en) * | 1988-12-09 | 1990-06-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of artificial stone fitted with pattern |
| JPH08174570A (en) * | 1994-12-21 | 1996-07-09 | Matsushita Electric Works Ltd | Patterning method of scagliola |
| JP2001114546A (en) * | 1999-10-15 | 2001-04-24 | Matsushita Electric Works Ltd | Method for producing artificial marble |
| WO2001098429A1 (en) * | 2000-06-22 | 2001-12-27 | Mitsubishi Rayon Co., Ltd. | Thickening agent, thickening composition and process for producing the same, sheet molding compound or bulk molding compound and process for producing the same, and molded resin and process for producing the same |
| KR20030044249A (en) * | 2001-11-29 | 2003-06-09 | 제일모직주식회사 | Method of Manufacturing Artificial Marble Having Inlay Pattern |
| JP2004263135A (en) * | 2003-03-04 | 2004-09-24 | Mitsubishi Rayon Co Ltd | (meth)acrylic resin composition, molded resin article and method for producing molded resin article |
| JP2008524020A (en) * | 2004-12-17 | 2008-07-10 | チェイル インダストリーズ インコーポレイテッド | Artificial marble having crack pattern and manufacturing method thereof |
| JP2016198889A (en) * | 2015-04-07 | 2016-12-01 | パナソニックＩｐマネジメント株式会社 | Method for producing artificial marble |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11905387B2 (en) | Functionalized graphene oxide curable formulations | |
| CN101802105B (en) | Liquid resin composition and cured product using the liquid resin composition | |
| CN104745055A (en) | High-strength coating formed by virtue of photo-thermal dual-curing and preparation method thereof | |
| US20060293449A1 (en) | Solid filler containing polymerizable compositions, articles formed thereby and methods of formation | |
| CN102807721B (en) | Impact modifier for polymethyl methacrylate resin having excellent impact strength and transparency and method of preparing the same | |
| CN103570275A (en) | Pure acrylic artificial stone as well as manufacturing method thereof | |
| CN103483995B (en) | A kind of PE gloss varnish and preparation method thereof | |
| CN109503954A (en) | A kind of PP composite material and its preparation method and application | |
| CN113388073A (en) | Photocurable flexible photosensitive resin, preparation method of photocurable flexible photosensitive resin, 3D printing product and preparation method of 3D printing product | |
| CN110183946A (en) | A kind of EB is coating material solidified, preparation method and applications | |
| CA2881476C (en) | Polymerisable mixture composition, use of the mixture composition and a dental prosthetic | |
| JP2017087527A (en) | Method for manufacturing artificial marble | |
| CN104893509A (en) | Photocuring paint for wood and preparation method thereof | |
| CN109096891A (en) | A kind of ultraviolet light solidification high rigidity woodwork coating and preparation method thereof | |
| JP2010528165A (en) | Reactive resin containing core-shell particles, method for producing the same and use thereof | |
| CN108559037A (en) | A kind of 3D printing photosensitive resin of nano modification and its preparation method and application | |
| CN108384492B (en) | Preparation method of PVC wood grain film adhesive | |
| JP6541058B2 (en) | Manufacturing method of artificial marble | |
| CN110272522A (en) | A kind of photosensitive resin material | |
| JP2635734B2 (en) | Production of patterned artificial stone | |
| CN108137899B (en) | Thermoplastic resin composition | |
| CN103601839B (en) | Acrylate copolymer levelling agent and preparation method thereof and the application process in wire enamel | |
| CN109320836A (en) | A kind of method of organic inorganic hybridization core-shell nano tenacity-increased profax | |
| JP4336936B2 (en) | Composition for soft resin molded article having excellent heat resistance and molded article obtained therefrom | |
| CN115246990B (en) | Double-component addition type room temperature vulcanization mold silicon rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151208 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20171220 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20171226 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180823 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190621 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190716 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20200303 |