JP2005290022A - Vinyl chloride-based resin paste for decorative sheet - Google Patents
Vinyl chloride-based resin paste for decorative sheet Download PDFInfo
- Publication number
- JP2005290022A JP2005290022A JP2004102449A JP2004102449A JP2005290022A JP 2005290022 A JP2005290022 A JP 2005290022A JP 2004102449 A JP2004102449 A JP 2004102449A JP 2004102449 A JP2004102449 A JP 2004102449A JP 2005290022 A JP2005290022 A JP 2005290022A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- resin paste
- viscosity
- based resin
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 90
- 229920005989 resin Polymers 0.000 title claims abstract description 90
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000004014 plasticizer Substances 0.000 claims abstract description 39
- 239000011256 inorganic filler Substances 0.000 claims abstract description 23
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000011164 primary particle Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 38
- 239000012855 volatile organic compound Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 14
- 239000003085 diluting agent Substances 0.000 abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000378 calcium silicate Substances 0.000 abstract description 3
- 229910052918 calcium silicate Inorganic materials 0.000 abstract description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004927 clay Substances 0.000 abstract description 3
- 229910052570 clay Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000000454 talc Substances 0.000 abstract description 3
- 229910052623 talc Inorganic materials 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 239000012749 thinning agent Substances 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- -1 saturated fatty acid ester Chemical class 0.000 description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- 101001120097 Homo sapiens Phosphatidylinositol 3-kinase regulatory subunit beta Proteins 0.000 description 1
- 102100026177 Phosphatidylinositol 3-kinase regulatory subunit beta Human genes 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、基材に塗布してビニル壁紙、床材等の内装建装材や家具等に被覆される化粧シートなどに用いられる装飾シート用塩化ビニル系樹脂ペーストに関する。詳しくは、該樹脂ペーストを基材に塗工して得られた装飾シートの製造工程、および得られた装飾シートからのＶＯＣ（Ｖｏｌａｔｉｌｅ Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄ：揮発性有機化合物）の放散が少ない装飾シート用塩化ビニル系樹脂ペーストに関する。 The present invention relates to a vinyl chloride resin paste for a decorative sheet, which is applied to a base material and used for a decorative sheet or the like coated on interior decoration materials such as vinyl wallpaper and flooring, or furniture. Specifically, a decorative sheet manufacturing process obtained by applying the resin paste to a substrate, and a decorative sheet chlorination with less emission of VOC (Volatile Organic Compound) from the resulting decorative sheet. The present invention relates to a vinyl resin paste.
ビニル壁紙などの素材である装飾シート用塩化ビニル系樹脂ペーストには、塩化ビニル系樹脂を主成分として、通常、可塑剤、希釈剤、二次可塑剤、充填剤、安定剤、顔料、難燃剤などが配合されている。
この塩化ビニル系樹脂ペーストを、ロータリースクリーン、コンマコーター、ロールコート、バーコートなどの塗布方法により、壁紙用などの基材の上に塗工し、表面に種々の印刷や凹凸模様などを施すことで装飾性を高め、このようにして得られるシート(装飾シート）が、壁紙などに用いられている。
Vinyl chloride resin paste for decorative sheets, which is a material such as vinyl wallpaper, is mainly composed of vinyl chloride resin, usually plasticizer, diluent, secondary plasticizer, filler, stabilizer, pigment, flame retardant Etc. are blended.
Apply this vinyl chloride resin paste on a base material for wallpaper, etc. by coating methods such as a rotary screen, comma coater, roll coat, bar coat, etc., and give various printing or uneven patterns on the surface. The sheet (decoration sheet) obtained in this way is used for wallpaper.
希釈剤や二次可塑剤は、塩化ビニル系樹脂ペーストの粘度を低化させて、生産効率の向上や製品不良等をなくすために添加されている。
しかし、従来の壁紙等の装飾シートにおいては、製造工程や得られた製品から塩化ビニル系樹脂ペースト中に配合された希釈剤や二次可塑剤などに含まれている揮発性の高い成分が、装飾シートから揮発することがあり、人体や環境に与える影響が懸念されている。
そのため、この揮発成分、すなわち揮発性有機化合物（Ｖｏｌａｔｉｌｅ Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄ；以下、ＶＯＣと記載することがある）の使用をできる限り減少させることが試みられ、樹脂ペースト中の配合剤の種類やその配合量を検討することがなされている。
Diluents and secondary plasticizers are added to reduce the viscosity of the vinyl chloride resin paste, thereby improving production efficiency and eliminating product defects.
However, in decorative sheets such as conventional wallpaper, highly volatile components contained in diluents and secondary plasticizers blended in the vinyl chloride resin paste from the manufacturing process and the resulting product, There is a concern that the decorative sheet may volatilize and affect the human body and the environment.
For this reason, attempts have been made to reduce the use of this volatile component, that is, a volatile organic compound (hereinafter sometimes referred to as VOC) as much as possible, and the type and amount of the compounding agent in the resin paste. Have been considered.
一方、揮発性成分を含む希釈剤や二次可塑剤を使用しない、またはその使用を減らした塩化ビニル系樹脂ペーストでは、樹脂ペーストの粘度が上昇してしまうため、塗工してシートを形成する際に、塗工に先立つ濾過操作の特性（濾過性）はもとより、塗工性においても、あるいは塗工スピード、その他の種々の作業性において問題が生じる。
加えて、粘性の高いペーストを用いた装飾シートでは、その平面平滑性に不具合を生じることもあり、製品不良となる可能性もある。
このような実情の下で、従来から、揮発成分を含む希釈剤や二次可塑剤を使用しなくとも、現行の塗工設備において塗工可能な塗料粘度を維持でき、かつ良好な塗工面を形成することのできる塩化ビニル系樹脂ペーストの開発が試みられている。
In addition, a decorative sheet using a paste having a high viscosity may cause a defect in the planar smoothness and may cause a product defect.
Under such circumstances, it is possible to maintain a coating viscosity that can be applied in the current coating equipment without using a diluent or secondary plasticizer containing a volatile component, and a good coating surface. Attempts have been made to develop a vinyl chloride resin paste that can be formed.
本発明は、以上の諸点を考慮し、塩化ビニル系樹脂ペースト中に（粘度を下げる目的で）揮発性成分を含む希釈剤や二次可塑剤を配合しなくても、現行の塗工設備において塗工可能な塗料粘度を示し、従って塗工性に優れ、良好な塗工面を形成することができると共に、VOC低放散製品（例えば、壁紙などの装飾シート）の素材となり得る装飾シート用塩化ビニル系樹脂ペーストを提供することを課題とする。 In consideration of the above points, the present invention can be applied to existing coating equipment without blending a diluent or secondary plasticizer containing a volatile component in the vinyl chloride resin paste (for the purpose of reducing the viscosity). Vinyl chloride for decorative sheets that shows paint viscosity that can be applied, and therefore has excellent coatability, can form a good coating surface, and can be used as a material for VOC low-emission products (for example, decorative sheets such as wallpaper). An object is to provide a resin paste.
上記の課題を解決するために、本発明者らは、VOC低放散製品を実現できる塩化ビニル系樹脂ペーストについて種々検討を行ったところ、まず、揮発性成分を含む希釈剤や二次可塑剤を使用しないことに着目し、（α）その揮発性成分を揮発しにくい減粘剤に置き換えることと、（β）この揮発しにくい減粘剤の選択を最適なものにすること、が塗工後の壁紙等の装飾シートから放散するＶＯＣ量を低減できるとの見知を得た。 In order to solve the above problems, the present inventors have made various studies on vinyl chloride resin pastes that can realize low VOC emission products. First, a diluent or secondary plasticizer containing a volatile component is used. Focusing on not using, (α) replacing the volatile component with a less volatile thinning agent and (β) optimizing the selection of this less volatile thinning agent after coating It has been found that the amount of VOC emitted from decorative sheets such as wallpaper can be reduced.
次に、この知見の下でさらに検討を重ねた結果、（γ）樹脂ペーストに使用する塩化ビニル系樹脂の性状、あるいは（δ）無機質充填剤の性状についても、それぞれ特定のものを選択することで、希釈剤や二次可塑剤を使用せずに減粘剤を使用することで、ペーストの低粘度化を図ることができることをも見出し、本発明を完成するに至った。 Next, as a result of further investigation under this knowledge, (γ) the properties of the vinyl chloride resin used in the resin paste or (δ) the properties of the inorganic filler should be selected. Thus, the present inventors have also found that the viscosity of the paste can be reduced by using a thinning agent without using a diluent or a secondary plasticizer, and the present invention has been completed.
すなわち、本発明は、少なくとも塩化ビニル系樹脂、減粘剤、可塑剤からなる装飾シート用塩化ビニル系樹脂ペーストであって、前記減粘剤の含有量が、塩化ビニル系樹脂１００重量部に対し５〜３５重量部であり、かつ該減粘剤は、沸点が２８０℃以上、または炭素数が１７以上であることを特徴とする装飾シート用塩化ビニル系樹脂ペーストを要旨とする。
このとき、（１）塩化ビニル系樹脂ペーストに使用する塩化ビニル系樹脂は、平均１次粒子径０．１〜２０μｍの粒度分布内で、粒径分布のピークが２〜４個有するものが好ましく、さらに（２）無機質充填剤は、比表面積が１５００〜４０００ｃｍ２／ｇのものが好ましく、通常使用されている無機質充填材が使用でき、例えば、炭酸カルシウム、水酸化アルミニウム、タルク、シリカ、クレー、珪酸カルシウム、アルミナ等であり、これらの無機質充填材は単独でも、あるいは適宜の組み合わせによる２種以上を混合使用しても良い。
That is, the present invention is a vinyl chloride resin paste for a decorative sheet comprising at least a vinyl chloride resin, a viscosity reducing agent, and a plasticizer, and the content of the viscosity reducing agent is 100 parts by weight of the vinyl chloride resin. The gist of the vinyl chloride resin paste for decorative sheets is 5 to 35 parts by weight, and the thinning agent has a boiling point of 280 ° C. or higher or a carbon number of 17 or higher.
At this time, (1) the vinyl chloride resin used in the vinyl chloride resin paste preferably has 2 to 4 particle size distribution peaks within a particle size distribution with an average primary particle size of 0.1 to 20 μm. Furthermore, (2) the inorganic filler preferably has a specific surface area of 1500 to 4000 cm 2 / g, and commonly used inorganic fillers can be used, for example, calcium carbonate, aluminum hydroxide, talc, silica, clay , Calcium silicate, alumina and the like, and these inorganic fillers may be used alone or in combination of two or more by an appropriate combination.
本発明では、塩化ビニル系樹脂ペースト中の減粘剤の含有量は、減粘効果、塗工性、塗工後の製品（壁紙等装飾シート）における性能面やＶＯＣ放散量などの観点から、塩化ビニル系樹脂１００重量部に対し５〜３５重量部とし、可塑剤や無機質充填剤の含有量（配合量）に応じて、この範囲内で適宜選定する。
減粘剤は、５重量部未満であると、減粘効果を得ることがむずかしく、３５重量部を超えると、減粘効果は飽和し、添加量を増やしても減粘効果の更なる向上を得ることはできないばかりか、使用する減粘剤によっては、ブリードアウトが発生し、ベタツキ等が発生してしまったり、発泡剤を使用した場合に発泡性能が阻害されることもある。
In the present invention, the content of the viscosity reducing agent in the vinyl chloride resin paste is from the viewpoint of the viscosity reduction effect, coating properties, performance in the product after coating (decorative sheet such as wallpaper), VOC emission amount, and the like. The amount is 5 to 35 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and is appropriately selected within this range according to the content (blending amount) of the plasticizer and inorganic filler.
If the viscosity reducing agent is less than 5 parts by weight, it is difficult to obtain a viscosity reducing effect. If it exceeds 35 parts by weight, the viscosity reducing effect is saturated, and even if the amount of addition is increased, the viscosity reducing effect can be further improved. Not only can it be obtained, but depending on the thinning agent used, bleeding out may occur, stickiness or the like may occur, or foaming performance may be impaired when a foaming agent is used.
そして、上記減粘剤は、標準圧力での沸点が２８０℃以上、または炭素数が１７以上のものを使用する。
この沸点が２８０℃以上、または炭素数が１７以上の減粘剤は、生産工程中、及び常温下において塗工後の製品から揮発するVOC量が低い。
このような減粘剤を用いることによって、本発明の樹脂ペーストによれば、VOCの放散が低い製品を得ることができる。
And the said thickener uses the thing whose boiling point in a standard pressure is 280 degreeC or more, or carbon number 17 or more.
A viscosity reducing agent having a boiling point of 280 ° C. or higher or a carbon number of 17 or higher has a low amount of VOC that volatilizes from a product after coating in the production process and at room temperature.
By using such a thickener, a product with low VOC emission can be obtained according to the resin paste of the present invention.
なお、上記の減粘剤の具体例としては、飽和脂肪酸エステル、不飽和脂肪酸エステル、カルボン酸エステル等からなる標準圧力での沸点が２８０℃以上、または炭素数が１７以上のものを使用する。例えば、可塑剤としても用いることができるアジピン酸ジイソノニル（ＤＩＮＡ）、植物油を主原料とした脂肪酸ブチル、パルミチン酸イソプロピル、ミリスチン酸イソプロピル、ソルビタンエステル、グリセリンアルキルエステル等が挙げられる。 In addition, as a specific example of said thickener, the boiling point in the standard pressure which consists of saturated fatty acid ester, unsaturated fatty acid ester, carboxylic acid ester, etc. is 280 degreeC or more, or a C17 or more thing is used. Examples thereof include diisononyl adipate (DINA) that can also be used as a plasticizer, fatty acid butyl, isopropyl palmitate, isopropyl myristate, sorbitan ester, glycerin alkyl ester, etc., mainly made from vegetable oil.
減粘剤の樹脂ペースト中への添加方法は、塩化ビニル系樹脂の重合終了時に添加してもよく、あるいは、ペースト調製時に同じ液状成分である可塑剤などと混合添加してもよく、添加方法において何ら制限されるものではない。 The method of adding the thinning agent into the resin paste may be added at the end of the polymerization of the vinyl chloride resin, or may be mixed and added with a plasticizer that is the same liquid component at the time of paste preparation. There are no restrictions on the above.
本発明における塩化ビニル系樹脂としては、ホモポリマーのポリ塩化ビニルの他に、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体、塩化ビニル−アクリル共重合体等のコポリマーをも使用することができ、これらは重合度が６５０〜１６５０程度のものを好ましく使用できる。
これらの塩化ビニル系樹脂は、いずれかを単独、あるいは適宜の組み合わせによる２種以上を混合して使用することができる。
As the vinyl chloride resin in the present invention, in addition to homopolymer polyvinyl chloride, copolymers such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-acrylic copolymer are also used. Those having a degree of polymerization of about 650 to 1650 can be preferably used.
These vinyl chloride resins can be used either alone or as a mixture of two or more thereof in an appropriate combination.
本発明では、この塩化ビニル系樹脂として、平均１次粒子径が０．１〜２０μｍ、かつ粒径分布のピークが２〜４個を有するものを用いることが好適である。平均１次粒子径が０．１μｍ未満であると、増粘傾向が大きくなるために、装飾シート用樹脂ペーストの調製作業が困難となり、２０μｍを超えると、ペーストレジンとして安定製造が困難となるとともに、スクリーン等の目詰まりが発生しやすくなり、コーターにおけるスジ不良（樹脂ペーストがコーターに筋状に付着すること）の発生する可能性も高くなり好ましくない。
また、粒径分布のピークが２〜４個有するものは、１個のピークを有するものに比べて、粒径の異なる大小の樹脂粒子が存在することで最密充填されやすく、可塑剤はこの最密充填状態の粒子間に入り込みにくくなるため、流動に寄与する可塑剤の量を減少させても、樹脂ペーストの増粘化を防止することが可能となる。この結果、本発明の目的である、希釈剤や二次可塑剤を使用せずに、揮発性の低い減粘剤を使用することのみであっても、塗工性をより一層優れたものとすることができ、良好な塗工面を形成することができる樹脂ペーストとなる。
In the present invention, it is preferable to use a vinyl chloride resin having an average primary particle size of 0.1 to 20 μm and 2 to 4 peaks in the particle size distribution. When the average primary particle size is less than 0.1 μm, the tendency to increase the viscosity becomes large, so that it is difficult to prepare a resin paste for decorative sheets, and when it exceeds 20 μm, stable production as a paste resin becomes difficult. This is not preferable because clogging of the screen or the like is likely to occur, and streak defects in the coater (the resin paste adheres to the coater in a streak shape) is also increased.
In addition, those having 2 to 4 particle size distribution peaks are more likely to be packed most closely due to the presence of large and small resin particles having different particle sizes compared to those having one peak. Since it becomes difficult to enter between particles in the close-packed state, it is possible to prevent the resin paste from thickening even if the amount of plasticizer contributing to flow is reduced. As a result, even if it is only the use of a low volatility thinning agent without using a diluent or secondary plasticizer, which is the object of the present invention, the coatability is further improved. Thus, the resin paste can form a good coated surface.
このように、上記の粒度分布の範囲内で、かつ粒径分布のピークが２〜４個有る塩化ビニル系樹脂を用いることにより、樹脂ペーストの増粘性を抑えることができため、本発明の樹脂ペーストは、VOC低放散製品の素材として好適である。 Thus, by using a vinyl chloride resin having 2 to 4 peaks in the particle size distribution within the above range of particle size distribution, it is possible to suppress the thickening of the resin paste. The paste is suitable as a material for a low VOC emission product.
無機質充填剤は、一般的に樹脂ペーストの強度や難燃性などの諸性質を改善するとともに、樹脂の使用量を低減し、コストダウンを図るために、必要に応じて添加される。
但し、通常は、無機質充填剤の添加により、樹脂ペーストが増粘傾向となり、本発明の阻害要因となるものである。そこで、本発明における無機質充填剤は、比表面積が１５００〜４０００ｃｍ２／ｇのものを使用することが好ましい。
Inorganic fillers are generally added as necessary to improve various properties such as strength and flame retardancy of the resin paste, reduce the amount of resin used, and reduce costs.
However, usually, the addition of the inorganic filler tends to increase the viscosity of the resin paste, which is an inhibiting factor of the present invention. Therefore, the inorganic filler in the present invention preferably has a specific surface area of 1500 to 4000 cm 2 / g.
この範囲内の比表面積を有する無機質充填剤であれば、樹脂ペーストの増粘傾向を低減することができる。比表面積が１５００ｃｍ２／ｇより小さいもの、すなわち粒径が大きい充填剤は、樹脂ペーストに添加した場合に沈降しやすく、濾過する際に目詰まりを発生し、ペーストの調製あるいは塗工段階において問題が生じる可能性が高くなる。一方、比表面積が４０００ｃｍ２／ｇより大きいものでは、粒径が微細すぎるため、樹脂ペーストが増粘してしまい、塗工スピード等が低下するという問題が発生し、減粘剤の増量や希釈剤の併用が必要となり、ＶＯＣ低減目的が達成できなくなる可能性がある。
従って、本発明では、上記のような比表面積を有する無機質充填剤を用いることが好ましく、これにより、樹脂ペーストの増粘性を抑えることができ、この結果として塩化ビニル系樹脂ペースト中における減粘剤の使用のみで、VOC低放散製品の素材として好適に使用することができ、生産性等においても問題ないものとなる。
If the inorganic filler has a specific surface area within this range, the tendency of thickening the resin paste can be reduced. A filler having a specific surface area smaller than 1500 cm 2 / g, that is, a filler having a large particle size, tends to settle when added to a resin paste, and clogging occurs during filtration, which is a problem in the preparation or coating stage of the paste. Is likely to occur. On the other hand, when the specific surface area is larger than 4000 cm 2 / g, the particle size is too fine, so that the resin paste is thickened and the coating speed is reduced. It is necessary to use a combination of agents, and the VOC reduction purpose may not be achieved.
Therefore, in the present invention, it is preferable to use an inorganic filler having the specific surface area as described above, whereby the thickening of the resin paste can be suppressed, and as a result, the thickening agent in the vinyl chloride resin paste. It is possible to use it as a material for a VOC low-emission product only by using it, and there is no problem in productivity.
本発明においては、上記の無機質充填剤として、炭酸カルシウム、水酸化アルミニウム、タルク、シリカ、クレー、珪酸カルシウム、アルミナ等を好ましく使用でき、これらは単独で使用してもよいし、適宜の組み合わせによる複数を併用してもよい。
上記の比表面積を有するこれらの無機質充填剤であれば、無機質充填剤添加による樹脂ペーストの増粘性を抑制することができ、本発明の目的を効果的に達成することができる。
In the present invention, calcium carbonate, aluminum hydroxide, talc, silica, clay, calcium silicate, alumina and the like can be preferably used as the inorganic filler, and these may be used alone or in an appropriate combination. A plurality may be used in combination.
With these inorganic fillers having the above specific surface area, the viscosity increase of the resin paste due to the addition of the inorganic filler can be suppressed, and the object of the present invention can be effectively achieved.
塩化ビニル系樹脂ペースト中の無機質充填剤の含有量は、装飾シートの所望の物性を得るために適宜の量で添加されるが、一般には、塩化ビニル系樹脂１００重量部に対し１０〜１５０重量部が好ましい。
１０重量部未満では、無機質充填剤を添加する効果があまり得られず、１５０重量部を超えると、塗工作業性に支障をきたす可能性がある。
The content of the inorganic filler in the vinyl chloride resin paste is added in an appropriate amount in order to obtain the desired physical properties of the decorative sheet, but generally 10 to 150 weights per 100 parts by weight of the vinyl chloride resin. Part is preferred.
If the amount is less than 10 parts by weight, the effect of adding the inorganic filler is not so much obtained. If the amount exceeds 150 parts by weight, the coating workability may be hindered.
本発明の塩化ビニル系樹脂ペーストに添加される可塑剤としては、通常使用されているものであればどのようなものでも使用できるが、ＶＯＣ対策の面からすると標準圧力での沸点が２８０℃以上のものを使用することが好ましい。 As the plasticizer added to the vinyl chloride resin paste of the present invention, any conventional plasticizer can be used, but the boiling point at standard pressure is 280 ° C. or higher from the viewpoint of VOC countermeasures. Are preferably used.
具体的には、減粘効果や含まれる揮発成分量を考慮して、フタル酸ジオクチル（ＤＯＰ）、フタル酸ジイソノニル（ＤＩＮＰ）等のフタル酸系可塑剤や、アジピン酸ジイソノニル（ＤＩＮＡ）などのアジピン酸系可塑剤等が使用でき、フタル酸系可塑剤を単独使用してもよいし、フタル酸系可塑剤とアジピン酸系可塑剤とを混合使用することもできる。
これらのフタル酸系およびアジピン酸系以外の可塑剤として、本発明では、粘度やその他の性状面からクエン酸アセチルトリブチル（ＡＴＢＣ）、グリセリンジアセトモノラウレート等も使用することができる。
ただし、アジピン酸系可塑剤は、本発明においては減粘剤として使用することができ、この使用量が３５重量部を超えるとベタツキ等の問題が発生するため、アジピン酸系以外のフタル酸系などの可塑剤を単独使用したり、あるいは２種以上を混合使用して、アジピン酸系可塑剤は減粘剤としての使用にとどめることが好ましい。
また、減粘剤として、アジピン酸系可塑剤以外のものを使用する場合においても、可塑剤としてのアジピン酸系可塑剤の使用量は、３５重量部以下とし、他の可塑剤を併用することが好ましい。
Specifically, in consideration of the viscosity reducing effect and the amount of volatile components contained, phthalic acid plasticizers such as dioctyl phthalate (DOP) and diisononyl phthalate (DINP), and adipine such as diisononyl adipate (DINA) An acid plasticizer or the like can be used, and a phthalic acid plasticizer can be used alone, or a phthalic acid plasticizer and an adipic acid plasticizer can be used in combination.
In the present invention, acetyl tributyl citrate (ATBC), glycerin diacetomonolaurate, and the like can also be used as plasticizers other than these phthalic acid and adipic acid based on viscosity and other properties.
However, the adipic acid plasticizer can be used as a viscosity reducing agent in the present invention, and if this amount exceeds 35 parts by weight, problems such as stickiness occur. It is preferable to use the adipic acid type plasticizer only as a thinning agent by using a plasticizer such as singly or in combination of two or more.
In addition, when using other than the adipic acid plasticizer as the thinning agent, the amount of the adipic acid plasticizer used as the plasticizer should be 35 parts by weight or less, and other plasticizers should be used in combination. Is preferred.
可塑剤の含有量は、所望の装飾シートを得るために適宜の量で添加される。通常は、塩化ビニル系樹脂１００重量部に対し、３５〜８０重量部が好ましく、製品の風合いを考慮し、使用する減粘剤や無機質充填剤の添加量に応じて、この含有量の範囲内で適宜選定することが好ましい。 The content of the plasticizer is added in an appropriate amount to obtain a desired decorative sheet. In general, it is preferably 35 to 80 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, considering the texture of the product, and within the range of this content depending on the amount of the thickener or inorganic filler used. It is preferable to select as appropriate.
上記可塑剤以外に、安定剤を適宜添加することができる。安定剤は、通常液状成分であり、塩化ビニル系樹脂ペーストの加工工程での熱による変質を防止するために、また発泡性装飾シートの場合においては発泡安定性のために、配合される。
安定剤としては、具体的には、バリウム系、カリウム系、亜鉛系等の安定剤が好ましく使用でき、液状である場合においては、標準圧力における沸点が２８０℃以上のものが好ましい。
安定剤の含有量は、塩化ビニル系樹脂１００重量部に対し１〜１０重量部が好ましい。
In addition to the plasticizer, a stabilizer can be appropriately added. The stabilizer is usually a liquid component, and is blended for preventing deterioration due to heat in the processing step of the vinyl chloride resin paste, and in the case of a foaming decorative sheet, for stabilizing foaming.
Specifically, a stabilizer such as barium-based, potassium-based, or zinc-based can be preferably used as the stabilizer, and in the case of a liquid, those having a boiling point of 280 ° C. or higher at standard pressure are preferable.
The content of the stabilizer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
さらに、顔料・染料等の着色剤、発泡剤、難燃剤、酸化防止剤をも、適宜添加することできる。これらは、通常の塩化ビニル系樹脂ペーストに配合する一般的なものが使用でき、用途に応じて適宜の量で添加することができる。 Furthermore, colorants such as pigments and dyes, foaming agents, flame retardants, and antioxidants can be added as appropriate. These may be those commonly used in ordinary vinyl chloride resin pastes and may be added in an appropriate amount depending on the application.
本発明の塩化ビニル系樹脂ペーストは、上記した各成分の所定量を、ブレンダー、ヘンシェルミキサー、ディスパー、ディゾルバー等を用い混合して得ることができる。 The vinyl chloride resin paste of the present invention can be obtained by mixing predetermined amounts of the above-described components using a blender, a Henschel mixer, a disper, a dissolver, or the like.
このようにして得られる本発明の装飾シート用塩化ビニル系樹脂ペーストは、壁紙をはじめ、各種の建飾材等に使用することができ、基材への塗工性に優れるばかりでなく、ＶＯＣ放散が少なく、ＶＯＣ低放散装飾シート用素材として好適なペーストであり、塗工性等の生産性おいて問題のなく使用することがでできる。 The vinyl chloride resin paste for decorative sheet of the present invention obtained in this way can be used for various kinds of decorative materials such as wallpaper and is not only excellent in coating property to a base material but also VOC. It is a paste that has little emission and is suitable as a VOC low emission decorative sheet material, and can be used without any problem in productivity such as coatability.
本発明における塩化ビニル系樹脂ペーストは、揮発性が高い成分を含有する希釈剤や二次可塑剤を使用することなく、減粘剤を使用するのみで、現行の混合設備、塗料搬送設備、塗工設備で製造できる粘度を有し、しかも塗工段階における塗工スピードを低下させない粘度を有する。
具体的な粘度として、本発明では、ＢＭ型粘度計、ローターＮｏ．４を用いて２５℃、６０ｒｐｍで測定した値が５００〜５０００ｍＰａ・ｓとすることが好ましい。
The vinyl chloride resin paste according to the present invention does not use a diluent or a secondary plasticizer containing a highly volatile component, but only uses a thinning agent, so that the current mixing equipment, paint transportation equipment, coating It has a viscosity that can be produced by a construction facility and has a viscosity that does not decrease the coating speed in the coating stage.
As a specific viscosity, in the present invention, a BM type viscometer, rotor No. The value measured at 25 ° C. and 60 rpm using 4 is preferably 500 to 5000 mPa · s.
本発明におけるVOC低放散製品とは、樹脂ペーストを塗工して得られたシートからの揮発成分の放散量が低減されるか否かが基準となる。
この揮発成分の放散量は、ＪＩＳ Ａ １９０１に基づく小型チャンバー試験で、１日後の放散量が４００μｇ／ｍ３以下のものがVOC低放散製品の素材として好適なペーストであり、本発明の装飾シート用塩化ビニル樹脂系ペーストはこれを満足するものである。
The VOC low emission product in the present invention is based on whether or not the emission amount of the volatile component from the sheet obtained by applying the resin paste is reduced.
The amount of volatile components emitted is a paste suitable for a VOC low emission product in a small chamber test based on JIS A 1901 with an emission amount of 400 μg / m 3 or less after one day. The vinyl chloride resin paste for use satisfies this.
本発明の塩化ビニル系樹脂ペーストは、揮発性の高い成分を含む希釈剤や二次可塑剤を使用することなく、沸点が２８０℃以上、または炭素数が１７以上である減粘剤を使用するのみで、現行の塗工設備において製造可能な塗料粘度を示し、塗工スピードを低下させることなく、しかも塗工性も良好で、良好な塗工面を有する製品を得ることができるので、VOCの放散が少ない壁紙等の装飾シートの素材として好適である。
このため、本発明の塩化ビニル系樹脂ペーストを使用して得られる塩化ビニル系樹脂シートは、壁紙、天井紙、家具類等の表面に貼着して使用される装飾シートにおいて、VOC低放散製品の実現をもたらすことができるものである。
The vinyl chloride resin paste of the present invention uses a viscosity reducing agent having a boiling point of 280 ° C. or higher or a carbon number of 17 or higher without using a diluent or secondary plasticizer containing a highly volatile component. The coating viscosity that can be produced with the current coating equipment alone, without lowering the coating speed, and with good coating properties and a product with a good coating surface can be obtained. It is suitable as a material for decorative sheets such as wallpaper with little diffusion.
For this reason, the vinyl chloride resin sheet obtained by using the vinyl chloride resin paste of the present invention is a VOC low-emission product in a decorative sheet used by being attached to the surface of wallpaper, ceiling paper, furniture, etc. Can be realized.
〔実施例および比較例〕
塩化ビニル樹脂に対して、減粘剤、可塑剤、無機質充填剤、および安定剤を表１に示す割合で配合し、ラボミキサーで均一に攪拌分散した後、減圧下で脱泡して、本発明の塩化ビニル系樹脂ペーストを調製した。
次に、これらの配合からなる各塩化ビニル系樹脂ペーストを、市販の壁紙用普通紙にコンマコーターを用いて２２０ｇ／ｍ２塗布し、乾燥させて、シートを得た。
[Examples and Comparative Examples]
Thickener, plasticizer, inorganic filler, and stabilizer are blended in the proportions shown in Table 1 with respect to the vinyl chloride resin, uniformly stirred and dispersed with a lab mixer, and then defoamed under reduced pressure. An inventive vinyl chloride resin paste was prepared.
Next, 220 g / m 2 of each vinyl chloride resin paste composed of these blends was applied to commercially available plain paper for wallpaper using a comma coater and dried to obtain a sheet.
各実施例および比較例において、塩化ビニル系樹脂ペーストの基材への塗工性、シートの表面仕上がり、シートのＶＯＣ放散量について、下記の内容で評価し、その結果を表１に示す。 In each of the examples and comparative examples, the coating properties of the vinyl chloride resin paste on the base material, the surface finish of the sheet, and the VOC emission amount of the sheet were evaluated according to the following contents, and the results are shown in Table 1.
（１）ペーストの安定性：各配合で得られた塩ビニル系樹脂ペーストについて、粘度、無機質充填剤の沈降性を考慮し、それぞれのペーストの安定性を評価した。
○：従来品と同様安定した塗料の性状を示し、特に問題ない。
△：若干増粘傾向、又は沈降傾向は見られるが、塗工工程での調整範囲である。
×：塗料の安定性が悪く、現状の設備では作業できない。
(1) Stability of paste: The stability of each paste was evaluated in consideration of the viscosity and the settling property of the inorganic filler for the vinyl chloride resin paste obtained in each formulation.
○: Stable paint properties similar to conventional products, no particular problem.
Δ: Slight thickening tendency or sedimentation tendency is observed, but the adjustment range in the coating process.
X: The stability of the paint is poor, and it is impossible to work with the current equipment.
（２）塗工性：各配合で得られた塩ビニル系樹脂ペーストについて、粘性を考慮し、それぞれの塗工性について評価を実施した。
○：従来品と同等に塗工でき、特に問題がない。
△：塗工時に多少の問題があるが、塗工自体に支障はない。
×：塗工できないか、生産性に問題がある。
(2) Coating properties: The vinyl chloride resin pastes obtained by the respective formulations were evaluated for each coating property in consideration of viscosity.
○: Coating can be performed in the same manner as conventional products, and there is no particular problem.
Δ: There are some problems during coating, but there is no problem in coating itself.
X: Cannot be applied or there is a problem in productivity.
（３）表面仕上がり：ペーストを塗工して得られたシートの表面状態を、スジ、裏抜け、ベトツキ等を考慮して総合的に評価した。
○：特に問題なし。
△：多少問題はあるが、製品として使用可能。
×：表面仕上がり的に問題があり、製品として使用できない。
(3) Surface finish: The surface state of the sheet obtained by applying the paste was comprehensively evaluated in consideration of streaks, back-through, stickiness, and the like.
○: No particular problem.
Δ: Although there is some problem, it can be used as a product.
X: There is a problem in the surface finish and it cannot be used as a product.
（４）ＶＯＣ放散量：得られたシートをＪＩＳ Ａ １９０１に基づく小型チャンバー試験で評価した。
○：１日後の放散量が４００μｇ／ｍ３以下。
×：１日後の放散量が４００μｇ／ｍ３を超えてしまう。
(4) VOC emission amount: The obtained sheet was evaluated by a small chamber test based on JIS A 1901.
○: The amount of emission after 1 day is 400 μg / m 3 or less.
X: Emission amount after 1 day exceeds 400 μg / m 3 .
表１における用語の意味は下記の通りである。
〔ポリ塩化ビニル樹脂〕
Ｐ８５Ｂ：新第一塩ビ（株）製、粒径分布が２個ピークを有し、各ピークの平均１次粒子径は０．３μｍ、２μｍである。
ＰＳＬ７００：鐘淵化学工業（株）製、粒径分布が３個ピークを有し、各ピークの平均１次粒子径は０．２μｍ、１．８μｍ、９μｍである。
Ｐ２４Ｚ：新第一塩ビ社製、粒径分布が１個ピークを有し、平均１次粒子径は０．８μｍである。
The meanings of terms in Table 1 are as follows.
[Polyvinyl chloride resin]
P85B: manufactured by Shin Daiichi Vinyl Co., Ltd., the particle size distribution has two peaks, and the average primary particle size of each peak is 0.3 μm and 2 μm.
PSL700: manufactured by Kaneka Chemical Co., Ltd., the particle size distribution has three peaks, and the average primary particle size of each peak is 0.2 μm, 1.8 μm, and 9 μm.
P24Z: manufactured by Shin-Daiichi PVC Co., Ltd., the particle size distribution has one peak, and the average primary particle size is 0.8 μm.
〔減粘剤〕
ＢＹ２０３８６：ビックケミー社製、沸点３２５℃以上（標準圧力：１０１．３ｋＰａ）
ＤＩＮＡ：（株）ジェイ・プラス製、沸点２２７℃（低圧力：０，６７ｋＰａ）
（なお、この値は標準圧力でのデータではなく、これを標準圧力に換算すると２８０℃以上と推測される。）
N−デカン：関東化学（株）製、沸点１７４℃（標準圧力：１０１．３ｋＰａ）
Ｎ−テトラデカン：関東化学（株）製、沸点２５３℃（標準圧力：１０１．３ｋＰａ）
[Thickener]
BY20386: manufactured by Big Chemie, boiling point of 325 ° C. or higher (standard pressure: 101.3 kPa)
DINA: manufactured by J Plus Co., Ltd., boiling point 227 ° C. (low pressure: 0.67 kPa)
(Note that this value is not the data at the standard pressure, but is estimated to be 280 ° C. or higher when converted to the standard pressure.)
N-decane: manufactured by Kanto Chemical Co., Inc., boiling point 174 ° C. (standard pressure: 101.3 kPa)
N-tetradecane: manufactured by Kanto Chemical Co., Inc., boiling point 253 ° C. (standard pressure: 101.3 kPa)
〔炭酸カルシウム〕
ＮＮ＃２００：日東粉化工業（株）製、比表面積１，５００ｃｍ２／ｇ
ＭＣ−３５：旭鉱末（株）製、比表面積３，５００ｃｍ２／ｇ
ＮＮ＃５００：日東粉化工業（株）製、比表面積５，０００ｃｍ２／ｇ
ＢＦ−４００：備北粉化工業（株）製、比表面積１，２００ｃｍ２／ｇ
[Calcium carbonate]
NN # 200: manufactured by Nitto Flour Industry Co., Ltd., specific surface area 1,500 cm 2 / g
MC-35: manufactured by Asahi Minesue Co., Ltd., specific surface area 3,500 cm 2 / g
NN # 500: manufactured by Nitto Flour Industry Co., Ltd., specific surface area of 5,000 cm 2 / g
BF-400: manufactured by Bihoku Flour Industry Co., Ltd., specific surface area 1,200 cm 2 / g
表１に示すように、本発明の実施例１〜６の装飾シート用塩化ビニル系樹脂ペーストは、ペーストの安定性、塗工性、表面仕上がり、ＶＯＣ放散量については、すべて優れていた。
また、比表面積の大きい無機質充填剤を添加した実施例７は、塗工性及び表面仕上がりが僅かに劣っており、比表面積の小さい無機質充填剤を用いた実施例８と粒径分布のピークが１個のポリ塩化ビニル樹脂を使用した実施例９は、ペーストの安定性と塗工性においても僅かに劣っていた。
これに対して、揮発性の高い成分を含む減粘剤を用いた比較例１及び比較例２は、ＶＯＣ放散量が目標値を超えており、減粘剤を添加しない比較例３は、ペーストの安定性、塗工性及び表面仕上がりが劣っており、減粘剤を多く添加した比較例４は、表面仕上がりが劣っており、また比較例４の減粘剤は、アジピン酸系可塑剤であるＤＩＮＡであり、しかもその配合量は、３５重量部を超えていたため、表面にベタツキが発生して、製品として問題があった。
As shown in Table 1, the vinyl chloride resin pastes for decorative sheets of Examples 1 to 6 of the present invention were all excellent in paste stability, coating properties, surface finish, and VOC emission.
Moreover, Example 7 which added the inorganic filler with a large specific surface area is slightly inferior in coating property and surface finish, and the peak of a particle size distribution is similar to Example 8 using the inorganic filler with a small specific surface area. Example 9 using one polyvinyl chloride resin was slightly inferior in paste stability and coatability.
On the other hand, Comparative Example 1 and Comparative Example 2 using a thinning agent containing a highly volatile component have a VOC emission amount exceeding the target value, and Comparative Example 3 without adding a thinning agent is a paste. Comparative Example 4 in which the stability, coating property and surface finish of the resin were inferior, and the surface finish was inferior in Comparative Example 4 to which a large amount of the viscosity reducing agent was added. Since it was a certain DINA and its blending amount exceeded 35 parts by weight, the surface was sticky and there was a problem as a product.
本発明による塩化ビニル系樹脂ペーストは、揮発性の高いＶＯＣ成分を含む希釈剤や二次可塑剤を使用せずに、現行の塗工設備において製造可能な塗料粘度を示すため、優れた塗工面を有し、加工後のＶＯＣ放散が少ないシートの製造を可能とする。
従って、この樹脂ペーストからなる塩化ビニル系樹脂シートは、壁紙、天井紙、床材、家具類の表面に貼り付けられる化粧シート等に使用される装飾シートにおいてVOCの放散が少ない製品の実現をもたらすことができるものである。
The vinyl chloride resin paste according to the present invention exhibits a coating viscosity that can be produced in the current coating equipment without using a diluent or secondary plasticizer containing a highly volatile VOC component. It is possible to manufacture a sheet with low VOC emission after processing.
Therefore, the vinyl chloride resin sheet made of this resin paste brings about the realization of products with less VOC emission in decorative sheets used for wallpaper, ceiling paper, flooring, decorative sheets to be attached to the surface of furniture, etc. It is something that can be done.
Claims (3)
前記減粘剤の含有量が、塩化ビニル系樹脂１００重量部に対し５〜３５重量部であり、かつ該減粘剤は、沸点が２８０℃以上、または炭素数が１７以上であることを特徴とする装飾シート用塩化ビニル系樹脂ペースト。 A vinyl chloride resin paste for a decorative sheet comprising at least a vinyl chloride resin, a viscosity reducer, and a plasticizer,
The content of the viscosity reducing agent is 5 to 35 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and the viscosity reducing agent has a boiling point of 280 ° C. or higher or a carbon number of 17 or higher. A vinyl chloride resin paste for decorative sheets.
The inorganic filler is added, according to claim 1 or 2 decorative sheet vinyl chloride resin paste according to, characterized in that a specific surface area 1500~4000cm 2 / g of the inorganic filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004102449A JP2005290022A (en) | 2004-03-31 | 2004-03-31 | Vinyl chloride-based resin paste for decorative sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004102449A JP2005290022A (en) | 2004-03-31 | 2004-03-31 | Vinyl chloride-based resin paste for decorative sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005290022A true JP2005290022A (en) | 2005-10-20 |
Family
ID=35323333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004102449A Pending JP2005290022A (en) | 2004-03-31 | 2004-03-31 | Vinyl chloride-based resin paste for decorative sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005290022A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509943C (en) * | 2007-05-11 | 2009-07-08 | 沈阳化工股份有限公司 | A kind of preparation method of polyvinyl chloride paste resin |
| JP2012025115A (en) * | 2010-07-27 | 2012-02-09 | Toppan Cosmo Inc | Wallpaper |
| US8691363B2 (en) | 2007-07-26 | 2014-04-08 | Pyn, S.A. De C.V. | Decorative and protective nonslip covering of multiple uses and the production process and composition thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02228349A (en) * | 1989-01-03 | 1990-09-11 | Deutsche Solvay Werke Gmbh | Material for protecting automobile floor, manufacture thereof, and method of rheological control of said material |
| JPH06305092A (en) * | 1993-02-26 | 1994-11-01 | Showa Kako Kk | Method for producing wall material made of chlorine-containing resin |
| JPH0825582A (en) * | 1994-07-15 | 1996-01-30 | Toppan Printing Co Ltd | Antibacterial wallpaper and manufacturing method thereof |
| JPH10176087A (en) * | 1996-12-19 | 1998-06-30 | Mitsubishi Chem Corp | Plastisol composition |
| JPH10231322A (en) * | 1997-02-18 | 1998-09-02 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based resin and paste sol composition using the same |
| JP2000109707A (en) * | 1998-10-05 | 2000-04-18 | Kao Corp | Paste resin composition |
| JP2001335696A (en) * | 2000-05-26 | 2001-12-04 | Kao Corp | Paste resin composition |
| JP2002194159A (en) * | 2000-12-25 | 2002-07-10 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based paste resin composition and disposable glove |
| JP2005029621A (en) * | 2003-07-08 | 2005-02-03 | Kaneka Corp | Polyvinyl chloride-based resin composition for paste-processing wall paper and vinyl wall paper comprising the same |
-
2004
- 2004-03-31 JP JP2004102449A patent/JP2005290022A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02228349A (en) * | 1989-01-03 | 1990-09-11 | Deutsche Solvay Werke Gmbh | Material for protecting automobile floor, manufacture thereof, and method of rheological control of said material |
| JPH06305092A (en) * | 1993-02-26 | 1994-11-01 | Showa Kako Kk | Method for producing wall material made of chlorine-containing resin |
| JPH0825582A (en) * | 1994-07-15 | 1996-01-30 | Toppan Printing Co Ltd | Antibacterial wallpaper and manufacturing method thereof |
| JPH10176087A (en) * | 1996-12-19 | 1998-06-30 | Mitsubishi Chem Corp | Plastisol composition |
| JPH10231322A (en) * | 1997-02-18 | 1998-09-02 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based resin and paste sol composition using the same |
| JP2000109707A (en) * | 1998-10-05 | 2000-04-18 | Kao Corp | Paste resin composition |
| JP2001335696A (en) * | 2000-05-26 | 2001-12-04 | Kao Corp | Paste resin composition |
| JP2002194159A (en) * | 2000-12-25 | 2002-07-10 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based paste resin composition and disposable glove |
| JP2005029621A (en) * | 2003-07-08 | 2005-02-03 | Kaneka Corp | Polyvinyl chloride-based resin composition for paste-processing wall paper and vinyl wall paper comprising the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509943C (en) * | 2007-05-11 | 2009-07-08 | 沈阳化工股份有限公司 | A kind of preparation method of polyvinyl chloride paste resin |
| US8691363B2 (en) | 2007-07-26 | 2014-04-08 | Pyn, S.A. De C.V. | Decorative and protective nonslip covering of multiple uses and the production process and composition thereof |
| JP2012025115A (en) * | 2010-07-27 | 2012-02-09 | Toppan Cosmo Inc | Wallpaper |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102089394A (en) | Coating composition with increased anti-blocking properties | |
| US6638998B2 (en) | Use of surfactants for improving the compatibility of inorganic pigments in aqueous coating compositions | |
| CN101522774B (en) | Plastisol compositions | |
| TW201141968A (en) | Improved low titanium dioxide coatings | |
| CN1489624A (en) | Water-based paint and wallpaper for wallpaper | |
| JP2008222493A (en) | Surface treated calcium carbonate and resin composition obtained by compounding the same | |
| CN1784434A (en) | VOC free latex coalescent systems | |
| KR102345310B1 (en) | Vinyl chloride polymer and preparation method thereof | |
| JP2005290022A (en) | Vinyl chloride-based resin paste for decorative sheet | |
| JP2013500381A (en) | Polymer composition comprising a high solvating plasticizer and a surfactant | |
| EP1930366A2 (en) | Low-color foam compositions | |
| JP5192470B2 (en) | Paste resin composition | |
| CN1158361C (en) | Aqueous paint composition | |
| CN101855275B (en) | Acrylic plastisol viscosity reducers | |
| JP4588915B2 (en) | Acrylic resin plastisol and acrylic resin molded products | |
| JP2005029621A (en) | Polyvinyl chloride-based resin composition for paste-processing wall paper and vinyl wall paper comprising the same | |
| JP2005232381A (en) | Plastisol composition with low total volatile organic compound generation | |
| JP2003301385A (en) | Wall paper | |
| JP4838448B2 (en) | Acrylic plastisol for rotary screen printing | |
| JP4071149B2 (en) | Additive for vinyl chloride paste resin | |
| CN101397377B (en) | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same | |
| JP4758108B2 (en) | Anti-sticking solution for agricultural vinyl chloride resin film | |
| JPH0625496A (en) | Plastisol composition | |
| JP2010168568A (en) | Vinyl-chloride based resin paste composition | |
| JP2006273981A (en) | Low viscosity paste resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20070214 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081016 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100406 |
|
| A521 | Written amendment |
Effective date: 20100602 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20101005 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101201 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110412 |