JP2648202B2 - Vinyl chloride plastisol composition - Google Patents
Vinyl chloride plastisol compositionInfo
- Publication number
- JP2648202B2 JP2648202B2 JP2841289A JP2841289A JP2648202B2 JP 2648202 B2 JP2648202 B2 JP 2648202B2 JP 2841289 A JP2841289 A JP 2841289A JP 2841289 A JP2841289 A JP 2841289A JP 2648202 B2 JP2648202 B2 JP 2648202B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- vinyl chloride
- viscosity
- inorganic filler
- particle size
- 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.)
- Expired - Lifetime
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 13
- 229920001944 Plastisol Polymers 0.000 title claims description 6
- 239000004999 plastisol Substances 0.000 title claims description 6
- 239000002245 particle Substances 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011256 inorganic filler Substances 0.000 claims description 29
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 18
- 239000004014 plasticizer Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 8
- 239000011362 coarse particle Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 238000005507 spraying Methods 0.000 description 16
- 230000000873 masking effect Effects 0.000 description 14
- 239000003973 paint Substances 0.000 description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 238000007665 sagging Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000000889 atomisation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 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
- HLFCGJSXMLQMMZ-UHFFFAOYSA-N 2-(3-ethyl-1-phenylheptoxy)carbonylbenzoic acid Chemical compound C=1C=CC=CC=1C(CC(CC)CCCC)OC(=O)C1=CC=CC=C1C(O)=O HLFCGJSXMLQMMZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000000391 Lepidium draba Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、可塑剤の海の中に粒子状の塩化ビニル系樹
脂と無機充填材が島状に分散した状態の塩化ビニルプラ
スチゾル組成物（以下、PVCゾルと略称する）に関す
る。本発明のPVCゾルは、自動車の耐チッピング塗料、
床裏アンダーコート、スプレーシーラなどとして利用さ
れる。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a vinyl chloride plastisol composition in which a particulate vinyl chloride resin and an inorganic filler are dispersed in the sea of a plasticizer in an island shape. Hereinafter, abbreviated as PVC sol). The PVC sol of the present invention is a chipping-resistant paint for automobiles,
Used as under floor undercoat, spray sealer, etc.
［従来の技術］ 例えば自動車の車体を飛石などから保護するために、
PVCゾルからなる耐チッピング塗料が利用されている。
この耐チッピング塗料は厚膜に塗布することが望まし
く、高粘度のものをエアレススプレーにより塗布するこ
とにより、約300μｍ程度の膜厚を確保している。そし
てプレヒートされてほぼ硬化状態となった後、中塗り塗
料が塗布され、中塗り塗料の乾燥工程で完全に硬化して
中塗り塗料と一体的に接合される。また、中塗り塗膜表
面に塗布される層間耐チッピング塗料も知られている。
この層間耐チッピング塗料は、中塗り塗膜表面に塗装さ
れて硬化後、その表面に上塗り塗料が塗装される。[Prior art] For example, in order to protect a car body from flying stones,
An anti-chipping paint made of PVC sol is used.
This anti-chipping paint is desirably applied to a thick film, and a high-viscosity one is applied by airless spray to secure a film thickness of about 300 μm. Then, after being preheated to a substantially cured state, an intermediate coating is applied, and is completely cured in a drying step of the intermediate coating to be integrally joined with the intermediate coating. Further, an interlayer chipping-resistant paint applied to the surface of an intermediate coating film is also known.
This interlayer anti-chipping paint is applied to the surface of the intermediate coating film and cured, and then the top coat is applied to the surface.
このようなPVCゾルは、粒子状の塩化ビニル系樹脂
と、液状の可塑剤と、無機充填材とを主成分としてい
る。そして、これらを所望の性能となるように配合し、
さらに接着付与剤、安定剤、有機溶剤などを添加したも
のが一般的である。このようなPVCゾルは、例えば特開
昭62−275169号、特開昭63−6103号などの公報に開示さ
れている。Such a PVC sol contains, as main components, a particulate vinyl chloride resin, a liquid plasticizer, and an inorganic filler. Then, these are blended to obtain the desired performance,
Further, those generally added with an adhesion promoter, a stabilizer, an organic solvent, and the like are generally used. Such PVC sols are disclosed in, for example, JP-A-62-275169 and JP-A-63-6103.
［発明が解決しようとする課題］ 上記した従来のPVCゾルにおいては、エアレススプレ
ーにて塗布されて形成された塗膜の表面の平滑性に劣
り、外観品質に劣るという不具合があった。[Problems to be Solved by the Invention] In the above-mentioned conventional PVC sol, there is a problem that the surface of a coating film formed by applying an airless spray is inferior in surface smoothness and inferior in appearance quality.
ところで、スプレーにより形成される塗膜の平滑性を
向上させるには、スプレー時の塗粒の微粒化を良くする
こと、および塗料のレベリング性を良くすることが効果
的であることが知られている。しかしながらエアレスス
プレーで塗布される高粘度の塗料の場合には、塗料自体
のレベリング性を期待することは困難であり、エアレス
スプレー時の微粒化の向上を図ることが必要である。ス
プレー時の微粒化を向上させるには、スプレー時の粘度
を低下させるとよい。PVCゾルの場合、可塑剤や溶剤な
どの配合量を多くすれば粘度を低下させることができる
が、厚膜に塗装した場合にタレが生じたり、塗膜物性に
支障が生じる場合もある。By the way, it is known that to improve the smoothness of a coating film formed by spraying, it is effective to improve the atomization of the coating particles during spraying and to improve the leveling property of the paint. I have. However, in the case of high-viscosity paint applied by airless spray, it is difficult to expect the leveling property of the paint itself, and it is necessary to improve atomization during airless spray. In order to improve atomization at the time of spraying, it is preferable to lower the viscosity at the time of spraying. In the case of a PVC sol, the viscosity can be reduced by increasing the amount of a plasticizer, a solvent, or the like. However, when a thick film is applied, sagging may occur or the physical properties of the coating film may be affected.
そこで本発明者らはPVCゾルの組成を詳細に検討し
た。その結果、従来のPVCゾルにおいては、塩化ビニル
系樹脂粒子と無機充填材粒子の粒径分布が全体に均一で
はなく、偏りが生じていることを発見した。例えば特開
昭62−275169号公報では、塩化ビニル系樹脂は0.1〜３
μｍの粒子と10〜60μｍの粒子とよりなり、３〜10μｍ
の粒子が欠落している。そして鋭意研究の結果、塩化ビ
ニル系樹脂粒子と無機充填材粒子の粒径分布を調整する
ことにより、PVCゾルの粘性挙動が大きく変動すること
を見出した。Then, the present inventors examined the composition of the PVC sol in detail. As a result, it has been found that, in the conventional PVC sol, the particle size distribution of the vinyl chloride resin particles and the inorganic filler particles is not uniform as a whole, but is uneven. For example, in JP-A-62-275169, a vinyl chloride resin is 0.1 to 3%.
consisting of particles of 10 μm and particles of 10 to 60 μm, 3 to 10 μm
Of particles are missing. As a result of diligent research, it was found that by adjusting the particle size distribution of the vinyl chloride resin particles and the inorganic filler particles, the viscosity behavior of the PVC sol greatly fluctuated.
そしてさらに研究を重ねた結果、最適な粒径分布を見
出して、エアレススプレー時に粘度が低下し、塗着後は
急激に粘度が上昇するPVCゾル組成物を完成した。しか
しながら、このPVCゾル組成物では、塗着後の粘度が高
いために、他の不具合が生じた。例えば、層間耐チッピ
ング塗料においては、中塗り塗膜をマスキングテープな
どでマスキングして必要な部分のみに耐チッピング塗料
を厚膜に塗布する。次いでウェット状態でマスキングテ
ープを除去した後加熱して耐チッピング塗料を硬化さ
せ、さらにその表面に上塗り塗料を塗布することとして
いる。ここで耐チッピング塗料に上記した新規PVCゾル
を用いた場合、塗着後の粘度が高いためにマスキングテ
ープを除去した後の流動が生じず、マスキングテープを
剥がした部分の耐チッピング塗膜の端面が垂直な壁状と
なってそのまま硬化する。したがって耐チッピング塗膜
の端末部分はエッジ状となる場合があった。As a result of further studies, they found an optimal particle size distribution, and completed a PVC sol composition in which the viscosity decreased during airless spraying, and the viscosity increased rapidly after application. However, this PVC sol composition had another problem because the viscosity after application was high. For example, in the case of an interlayer chipping-resistant paint, the intermediate coating film is masked with a masking tape or the like, and the thick film is coated with the chipping-resistant paint only on necessary portions. Then, after removing the masking tape in a wet state, the chipping-resistant paint is cured by heating, and an overcoat is applied to the surface. Here, when the above-mentioned novel PVC sol is used as the chipping-resistant coating, the flow after removing the masking tape does not occur due to the high viscosity after application, and the end surface of the chipping-resistant coating film at the portion where the masking tape is removed. Becomes a vertical wall and cures as it is. Therefore, the end portion of the chipping-resistant coating film sometimes has an edge shape.
エッジ状の部分に液状の塗料を塗布すると、表面張力
によりエッジ部分の膜厚が小さくなることが知られてい
る。上記層間耐チッピング塗膜においても同様の現象が
生じ、そのためエッジ部分に上塗り塗料のスケが生じて
意匠性が損なわれる場合があった。It is known that when a liquid paint is applied to an edge-shaped portion, the film thickness of the edge portion becomes small due to surface tension. The same phenomenon occurs in the above-mentioned interlayer chipping-resistant coating film, and therefore, there is a case where an overcoating is caused at an edge portion to deteriorate the design property.
本発明はこのような事情に鑑みてなされたものであ
り、PVCゾルの粘性挙動を改良して、エアレススプレー
時には粘度を低下させ、塗着後に粘度が上昇するととも
に、マスキングテープを剥がす程度の剪断応力でも粘度
が低下するように構成することを目的とする。The present invention has been made in view of such circumstances, and improves the viscosity behavior of a PVC sol, reduces the viscosity during airless spraying, increases the viscosity after coating, and causes the masking tape to peel off to the extent that the masking tape is peeled off. It is an object of the present invention to configure so that the viscosity is reduced even under stress.
［課題を解決するための手段］ 本発明者らは粒子状物の粒径を最適にしたPVCゾルに
ついて、その組成をさらに詳細に検討した。その結果、
全体の粒径分布をその最適値に維持しつつ無機充填材の
粒径をさらに調整することにより、剪断速度−粘度の曲
線形状が変化することを見出して本発明を完成したもの
である。[Means for Solving the Problems] The present inventors have studied in more detail the composition of a PVC sol in which the particle size of the particulate matter is optimized. as a result,
The present invention has been completed by finding that the curve shape of the shear rate-viscosity changes by further adjusting the particle size of the inorganic filler while maintaining the entire particle size distribution at the optimum value.
すなわち本発明のPVCゾルは、粒子状の塩化ビニル系
樹脂と、粒子状の無機充填材と、可塑剤と、を主成分と
する塩化ビニルプラスチゾル組成物において、 塩化ビニル系樹脂と無機充填材の合計重量を100とし
た場合に塩化ビニル系樹脂と無機充填材とよりなる全粒
子の粒径の分布が２μｍ未満の微粒子20〜35重量％、２
μｍ以上で10μｍ未満の中粒子25〜40重量％、10μｍ以
上の粗粒子30〜50重量％となるように構成するととも
に、 無機充填材の重量を100とした場合に無機充填材の粒
径の分布が0.2μｍ未満の超微粒充填材25〜35重量％、
0.2μｍ以上で15μｍ未満の中粒充填材30〜45重量％、1
5μｍ以上の粗粒充填材25〜40重量％となるように構成
されたことを特徴とする。That is, the PVC sol of the present invention is a vinyl chloride plastisol composition containing a particulate vinyl chloride resin, a particulate inorganic filler, and a plasticizer as main components. When the total weight is 100, the particle size distribution of all particles composed of a vinyl chloride resin and an inorganic filler is less than 2 μm 20 to 35% by weight,
When the weight of the inorganic filler is 100 and the particle size of the inorganic filler is 100, the particle size of the inorganic filler is from 25 to 40% by weight of the medium particles of 25 μm or more and less than 10 μm, and 30 to 50% by weight of the coarse particles of 10 μm or more. 25-35% by weight of ultrafine filler having a distribution of less than 0.2 μm,
30 to 45% by weight of medium-sized filler of 0.2 μm or more and less than 15 μm, 1
It is characterized in that it is constituted so that the coarse filler of 5 μm or more is 25 to 40% by weight.
本発明のPVCゾルは、塩化ビニル系樹脂と、無機充填
材と、可塑剤とを主成分とする。塩化ビニル系樹脂とし
ては、乳化重合により製造されたペースト用塩化ビニル
樹脂、懸濁重合により製造されたブレンド用塩化ビニル
樹脂、あるいは塩化ビニル−酢酸ビニル系コポリマーな
どの塩化ビニル共重合体など、従来公知のプラスチゾル
用の樹脂が用いられる。その形状は粒子状である。The PVC sol of the present invention contains a vinyl chloride resin, an inorganic filler, and a plasticizer as main components. Conventional vinyl chloride resins include vinyl chloride resins for pastes produced by emulsion polymerization, vinyl chloride resins for blends produced by suspension polymerization, and vinyl chloride copolymers such as vinyl chloride-vinyl acetate copolymers. A known resin for plastisol is used. Its shape is particulate.
無機充填材としては、炭酸カルシウム、クレイ、シリ
カ、珪酸カルシウム、珪酸マグネシウム、珪酸アルミニ
ウム、炭酸マグネシウム、硫酸バリウム、カーボンブラ
ック、アスベスト、ケイソウ土、マイカ粉などを用いる
ことができる。他に酸化チタン、黄鉛などの着色顔料を
用いてもよい。この無機充填材の配合量は、塩化ビニル
系樹脂100重量部に対して100〜180重量部が最適であ
る。無機充填材の配合量がこの範囲を超えると物性が低
下するようになる。Examples of the inorganic filler include calcium carbonate, clay, silica, calcium silicate, magnesium silicate, aluminum silicate, magnesium carbonate, barium sulfate, carbon black, asbestos, diatomaceous earth, and mica powder. In addition, coloring pigments such as titanium oxide and graphite may be used. The optimal amount of the inorganic filler is 100 to 180 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount of the inorganic filler exceeds this range, the physical properties will decrease.
可塑剤としては室温で液体のものが用いられ、DOP、D
BPを始めとして、LBP、BBP、2EHBP、DIDP、DOA、DOS、D
OZ、TOF、DIDP、TCP、など従来と同様に用いることがで
きる。この可塑剤の配合量は、塩化ビニル系樹脂100重
量部に対して80〜160重量部が最適である。可塑剤の配
合量が80重量部より少ないとPVCゾルの粘度が高くなり
過ぎて塗膜の平滑性が低下し、160重量部より多くなる
と粘度が低くなり過ぎて厚膜に塗装するのが困難とな
る。A plasticizer that is liquid at room temperature is used, and DOP, D
Starting with BP, LBP, BBP, 2EHBP, DIDP, DOA, DOS, D
OZ, TOF, DIDP, TCP, etc. can be used in the same manner as before. The optimal amount of the plasticizer is 80 to 160 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount of the plasticizer is less than 80 parts by weight, the viscosity of the PVC sol becomes too high and the smoothness of the coating film is reduced, and if it is more than 160 parts by weight, the viscosity becomes too low and it is difficult to apply to a thick film. Becomes
なお、本発明のPVCゾルには、例えば接着付与剤、安
定剤、難燃剤、界面活性剤、有機溶剤など、従来公知の
各種添加剤を従来と同様に配合することができる。In the PVC sol of the present invention, conventionally known various additives such as an adhesion promoter, a stabilizer, a flame retardant, a surfactant, and an organic solvent can be blended in the same manner as in the conventional case.
本発明の一つの特徴は、塩化ビニル系樹脂と無機充填
材の粒径分布を規定したところにある。すなわち、塩化
ビニル系樹脂と無機充填材の合計重量を100とした場合
に、塩化ビニル系樹脂と無機充填材とよりなる全粒子の
粒径の分布が、２μｍ未満の微粒子20〜35重量％、２μ
ｍ以上で10μｍ未満の中粒子25〜40重量％、10μｍ以上
の粗粒子30〜50重量％となるように構成されている。粒
径の分布がこの範囲から外れると、エアレススプレー時
の粘度が高くなって塗面の平滑性に不具合が生じたり、
塗着後の粘度が低過ぎてタレか生じるため厚膜に塗装す
るのが困難となる場合がある。One feature of the present invention resides in that the particle size distribution of the vinyl chloride resin and the inorganic filler is specified. That is, assuming that the total weight of the vinyl chloride resin and the inorganic filler is 100, the particle size distribution of all particles composed of the vinyl chloride resin and the inorganic filler is 20 to 35% by weight of fine particles having a particle size of less than 2 μm, 2μ
It is configured so that the content of the medium particles is at least 25 to 40% by weight and the size of the coarse particles having a size of at least 10 μm is from 30 to 50% by weight. If the particle size distribution is out of this range, the viscosity at the time of airless spraying will increase and the smoothness of the coated surface will be impaired,
In some cases, the viscosity after coating is so low that sagging occurs, making it difficult to apply a thick film.
本発明の最大の特徴は、全体の粒径分布を上記値に維
持しつつ、無機充填材の重量を100とした場合に無機充
填材の粒径の分布が0.2μｍ未満の超微粒充填材25〜35
重量％、0.2μｍ以上で15μｍ未満の中粒充填材30〜45
重量％、15μｍ以上の粗粒充填材25〜40重量％となるよ
うに構成したところにある。このように構成することに
より、エアレススプレー時および塗着時の粘度を適性に
維持しつつ、マスキングテープを剥がす時に作用する程
度の剪断応力でも粘度が低下するように、剪断速度−粘
度曲線の形状が変化する。したがってマスキングテープ
を剥がす際にその部分が流動し、エッジ部分が生じず端
面は滑らかな曲面形状となる。The greatest feature of the present invention is that, while maintaining the entire particle size distribution at the above value, the particle size distribution of the inorganic filler is less than 0.2 μm when the weight of the inorganic filler is set to 100. ~ 35
30% to 45% by weight, medium-grained filler of 0.2 to less than 15 μm
%, That is, 25 to 40% by weight of a coarse filler having a particle size of 15 μm or more. With such a configuration, the shape of the shear rate-viscosity curve is adjusted such that the viscosity is reduced even with a shear stress acting when the masking tape is peeled off while maintaining the viscosity during airless spraying and coating appropriately. Changes. Therefore, when the masking tape is peeled off, the portion flows, and no edge portion is formed, and the end surface has a smooth curved surface shape.
［発明の作用および効果］ 本発明のPVCゾルでは、PVCゾル中に存在する粒子成分
全体の粒径の分布が上記範囲にあることにより、エアス
プレー時など高剪断応力が作用した時に粘度が急激に低
下する。これによりエアレススプレー時に吐出される塗
粒の微粒化に優れ、平滑な塗面が得られる。そして塗着
後には粘度が急激に上昇するため、厚膜に塗装してもタ
レなどの不具合が生じない。また、同一粘度とする場
合、可塑剤などの液体成分の量を最も少なくすることが
できる。これにより物性の向上を図ることができる。な
お、これらの作用はPVCゾル内に存在する全体の粒子成
分がPVCゾル内で最密充填構造を形成することに起因す
るものと推察される。[Operation and Effect of the Invention] In the PVC sol of the present invention, the viscosity is sharply increased when a high shear stress is applied such as during air spraying, because the distribution of the particle size of the entire particle component present in the PVC sol is within the above range. To decline. As a result, the coating particles discharged during airless spraying are excellent in atomization, and a smooth coating surface can be obtained. Then, since the viscosity sharply increases after coating, problems such as sagging do not occur even when coating on a thick film. When the viscosity is the same, the amount of a liquid component such as a plasticizer can be minimized. Thereby, the physical properties can be improved. These effects are presumed to be due to the fact that all the particle components present in the PVC sol form a close-packed structure in the PVC sol.
したがって本発明のPVCゾルによれば、エアレススプ
レー時の微粒化と、タレ防止という背反事象が両方とも
満足され、塗面が平滑で物性に優れた塗膜を厚膜に形成
することができる。Therefore, according to the PVC sol of the present invention, both the atomization during airless spraying and the reversal of sagging prevention are satisfied, and a coating film having a smooth coated surface and excellent physical properties can be formed into a thick film.
そして本発明のPVCゾルでは、無機充填材の粒径を調
整したことにより、比較的小さな剪断応力が作用した場
合でも粘度が低下する。したがってマスキングテープを
剥がす時に作用する剪断応力によっても粘度が低下する
ので、層間耐チッピング塗料として塗布された場合に、
マスキング除去時に端面が流動し、エッジ部分のない曲
面状の端面となる。したがって上塗り塗料を塗装した場
合の塗装見切り線のスケを防止することができる。In the PVC sol of the present invention, by adjusting the particle size of the inorganic filler, the viscosity is reduced even when a relatively small shear stress is applied. Therefore, the viscosity is also reduced by the shear stress acting when peeling off the masking tape, so when applied as an interlayer chipping-resistant paint,
At the time of masking removal, the end face flows, and becomes a curved end face without an edge portion. Therefore, it is possible to prevent invisibility of the parting line when the top coat is applied.
［実施例］ 以下、実施例により本発明を具体的に説明する。EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples.
（実施例１） 第１表にも示すように、塩化ビニル系樹脂全体を100
とした場合、粒径２μｍ未満の微粒子塩化ビニル樹脂
（「ペーストレジン」鐘淵化学工業製）26重量％と、粒
径２〜10μｍの中粒子塩化ビニル樹脂（「ペーストレジ
ン」鐘淵化学工業製）39重量％および粒径10μｍ以上の
粗粒子塩化ビニル樹脂（「ブレンドレジン」日本ゼオン
製）35重量％より塩化ビニル系樹脂を構成した。また、
無機充填材全体を100とした場合、粒径0.2μｍ未満の超
微粒炭酸カルシウム（コロイダル炭酸カルシウム）30重
量％と、粒径0.2〜15μｍの中粒炭酸カルシウム（重質
炭酸カルシウム）40重量％と、粒径15μｍ以上の粗粒炭
酸カルシウム（重質炭酸カルシウム）30重量％と、から
無機充填材を構成した。この塩化ビニル系樹脂100重量
部と、無機充填材130重量部と、可塑剤としての２エチ
ルヘキシルベンジルフタレート（2EHBP）120重量部、お
よび接着付与剤としてのポリアミノアマイドを３重量
部、安定剤としてのカルシウム石ケンを10重量部、さら
に溶剤としてミネラルスピリットを10重量部混合して本
実施例のPVCゾルを製造した。このPVCゾル内には、粒子
全体の合計重量を100とした場合、粒径２μｍ未満の微
粒子が28重量％、粒径２〜10μｍの中粒子が37重量％お
よび粒径10μｍ以上の粗粒子が35重量％の組成で含有さ
れている。(Example 1) As shown in Table 1, the total amount of the vinyl chloride resin was 100%.
26% by weight of fine-particle vinyl chloride resin having a particle size of less than 2 μm (“Paste Resin” manufactured by Kaneka Chemical Co., Ltd.) and medium-particle vinyl chloride resin having a particle size of 2 to 10 μm (“Paste Resin” manufactured by Kaneka Chemical Co., Ltd.) The vinyl chloride resin was composed of 39% by weight and 35% by weight of a coarse vinyl chloride resin having a particle size of 10 μm or more (“Blend Resin” manufactured by Nippon Zeon). Also,
When the total amount of the inorganic filler is 100, 30% by weight of ultrafine calcium carbonate (colloidal calcium carbonate) having a particle size of less than 0.2 μm, and 40% by weight of medium calcium carbonate (heavy calcium carbonate) having a particle size of 0.2 to 15 μm And 30% by weight of coarse calcium carbonate (heavy calcium carbonate) having a particle size of 15 μm or more, thereby constituting an inorganic filler. 100 parts by weight of this vinyl chloride resin, 130 parts by weight of an inorganic filler, 120 parts by weight of 2-ethylhexylbenzyl phthalate (2EHBP) as a plasticizer, 3 parts by weight of polyaminoamide as an adhesion promoter, 3 parts by weight as a stabilizer 10 parts by weight of calcium soap and 10 parts by weight of mineral spirit as a solvent were mixed to produce a PVC sol of this example. In this PVC sol, assuming that the total weight of all the particles is 100, 28% by weight of fine particles having a particle size of less than 2 μm, 37% by weight of medium particles having a particle size of 2 to 10 μm, and coarse particles having a particle size of 10 μm or more are included. It is contained in a composition of 35% by weight.
このPVCゾルについては、粘度、エアレススプレー適
性、タレ膜厚、上塗り塗料のスケおよび耐チッピング性
を測定および試験し、結果を第１表に示す。ここで、粘
度は剪断速度10S-1と剪断速度10000S-1における粘度を
測定した。10S-1の粘度は高い方が、10000S-1の粘度は
低い方が好ましい。This PVC sol was measured and tested for viscosity, suitability for airless spraying, sagging film thickness, scale and chipping resistance of the top coat, and the results are shown in Table 1. Here, the viscosity was measured for viscosity at a shear rate of 10S -1 and a shear rate of 10000s -1. It is preferable that the viscosity of 10S -1 is higher and the viscosity of 10,000S -1 is lower.
エアレススプレー適性は、塗装圧力120kg/cm2でエア
レススプレー塗装した時の、塗面の平滑性を目視で判定
し、基準板より平滑なものを○とした。The suitability for airless spraying was determined by visually observing the smoothness of the coated surface when airless spray coating was performed at a coating pressure of 120 kg / cm 2 , and the surface smoother than the reference plate was evaluated as ○.
タレ膜厚は上記の条件でエアレススプレー塗装した時
に、タレが生じない最大の膜厚を測定した。For the sagging film thickness, the maximum film thickness that does not cause sagging when airless spray coating was performed under the above conditions was measured.
上塗り塗料のスケは、マスキングテープを部分的に貼
着した鋼板表面にPVCゾルを300μｍの膜圧で塗布し、ウ
ェット状態でマスキングテープを剥がす。次いで100℃
で10分間加熱してPVCゾルを硬化させた後、白色上塗り
塗料をエアスプレーで全体に均一に35μｍの厚さとなる
ように塗布する。その時のPVCゾル塗膜の見切り線に生
じるスケを目視で判定し、スケが生じないものを○とし
た。For the scale of the top coat, a PVC sol is applied at a film pressure of 300 μm to the surface of the steel sheet on which the masking tape is partially adhered, and the masking tape is peeled off in a wet state. Then 100 ° C
After curing the PVC sol by heating for 10 minutes, a white top coat is applied by air spray to a uniform thickness of 35 μm. At that time, the scale generated on the parting line of the PVC sol coating film was visually determined.
耐チッピング性は、上記PVCゾルを電着塗装された試
験鋼板表面に膜厚30μｍとなるように塗装し、140℃で4
0分間乾燥して硬化した塗膜に、2mの高さからナットを
落下させ素地が表出した際のナットの総重量を測定し
た。The chipping resistance is as follows. The above PVC sol is coated on the surface of the test steel plate which has been electrodeposited so as to have a thickness of 30 μm.
The nut was dropped from a height of 2 m onto the coating film dried and hardened for 0 minutes, and the total weight of the nut when the substrate was exposed was measured.
そして、これらの結果を総合的に評価して結果を第１
表に示す。These results are comprehensively evaluated and the
It is shown in the table.
（実施例２〜５、比較例１〜２） 第１表に示すように、塩化ビニル樹脂および炭酸カル
シウムの粒径分布を種々変化させたこと以外は実施例１
と同様にして、実施例２〜５および比較例１〜２のPVC
ゾルを製造した。そしてそれぞれのPVCゾルについて実
施例１と同様に測定および試験を行ない、結果を第１表
に示す。(Examples 2 to 5, Comparative Examples 1 and 2) As shown in Table 1, Example 1 except that the particle size distributions of the vinyl chloride resin and calcium carbonate were variously changed.
In the same manner as described above, the PVC of Examples 2 to 5 and Comparative Examples 1 to 2
A sol was produced. The measurements and tests were performed on each PVC sol in the same manner as in Example 1, and the results are shown in Table 1.
（評価） 第１表に示されるように、実施例１〜４で示される本
発明のPVCゾルは、10S-1の粘度が高く、かつ10000S-1の
粘度が低い。すなわち高いチクソトロピー性を示してい
る。これにより、エアレススプレー時には粘度が低下し
て微粒化されるため、塗面の平滑性（エアレススプレー
適性）に優れている。また、塗着後は急激に粘度が上昇
するため、高いタレ膜厚を有している。さらに、マスキ
ングテープを剥がした時の応力により粘度が低下して流
動するため、塗装見切り線のスケが生じない。そして耐
チッピング性能は従来と同様に好ましい範囲にある。(Evaluation) As shown in Table 1, PVC sols of the present invention shown in Examples 1-4, high viscosity 10S -1, and a low viscosity 10000s -1. That is, it shows high thixotropy. As a result, during airless spraying, the viscosity is reduced and the particles are atomized, so that the coating surface is excellent in smoothness (airless spray suitability). Further, since the viscosity sharply increases after coating, it has a high sagging film thickness. Further, the viscosity at the time of peeling off the masking tape causes the viscosity to decrease and flow, so that there is no invisibility of the parting line. The chipping resistance is in a preferable range as in the conventional case.
一方、比較例のPVCゾルでは、実施例に比べて10S-1の
粘度と10000S-1の粘度との差が小さく、エアレススプレ
ー適性の良いものは塗着後も粘度の上昇が小さくタレや
すくなっている。また、塗着後タレにくいものはエアレ
ススプレー適性に劣っている。そして比較例１〜２のPV
Cゾルでは、全体の粒径分布は本発明の範囲にあるもの
の、炭酸カルシウムの粒径分布が本発明の範囲から外れ
ている。そのためマスキングテープを剥がす際の剪断応
力では流動が困難となり、塗装見切り線がエッジ状とな
ってスケが発生している。On the other hand, the PVC sol of Comparative Example, the difference between the viscosity of the viscosity of the 10S -1 and 10000s -1 compared with Example is small, having good airless spray aptitude becomes easier sagging small increase after coating deposition the viscosity ing. Those that are difficult to sag after coating are inferior in airless spray suitability. And PV of Comparative Examples 1-2
In the case of the C sol, the overall particle size distribution falls within the range of the present invention, but the particle size distribution of calcium carbonate falls outside the range of the present invention. For this reason, it becomes difficult to flow due to the shearing stress when the masking tape is peeled off, and the parting line of the paint becomes edge-shaped, causing invisibility.
すなわち、実施例と比較例のPVCゾルにおけるこの性
能の差異は、塩化ビニル系樹脂の粒径と無機充填材の粒
径の分布によるものであることが明らかである。That is, it is clear that this difference in performance between the PVC sols of the example and the comparative example is due to the distribution of the particle size of the vinyl chloride resin and the particle size of the inorganic filler.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中間 信也 神奈川県横須賀市田浦港町無番地 関東 自動車工業株式会社内 (72)発明者 桜井 正敏 神奈川県横須賀市田浦港町無番地 関東 自動車工業株式会社内 (56)参考文献 特開 平２−208348（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinya Naka Nakano, Taura Port Town, Yokosuka City, Kanto Auto Works, Ltd. 56) References JP-A-2-208348 (JP, A)
Claims (1)
機充填材と、可塑剤と、を主成分とする塩化ビニルプラ
スチゾル組成物において、 前記塩化ビニル系樹脂と前記無機充填材の合計重量を10
0とした場合に前記塩化ビニル系樹脂と前記無機充填材
とよりなる全粒子の粒径の分布が２μｍ未満の微粒子20
〜35重量％、２μｍ以上で10μｍ未満の中粒子25〜40重
量％、10μｍ以上の粗粒子30〜50重量％となるように構
成するとともに、 前記無機充填材の重量を100とした場合に前記無機充填
材の粒径の分布が0.2μｍ未満の超微粒充填材25〜35重
量％、0.2μｍ以上で15μｍ未満の中粒充填材30〜45重
量％、15μｍ以上の粗粒充填材25〜40重量％となるよう
に構成されたことを特徴とする塩化ビニルプラスチゾル
組成物。1. A vinyl chloride plastisol composition comprising a particulate vinyl chloride resin, a particulate inorganic filler, and a plasticizer as main components, wherein the total of said vinyl chloride resin and said inorganic filler is Weight 10
When the particle diameter distribution of all the particles composed of the vinyl chloride resin and the inorganic filler is less than 2 μm,
35 to 40% by weight of medium particles 25 to 40% by weight, coarse particles of 10 μm or more and 30 to 50% by weight, and when the weight of the inorganic filler is 100, 25-35% by weight of ultrafine filler having a particle size distribution of inorganic filler of less than 0.2μm, 30-45% by weight of medium-size filler of 0.2μm or more and less than 15μm, and 25-40% of coarse-particle filler of 15μm or more A vinyl chloride plastisol composition, characterized in that the composition is constituted so as to give a weight percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2841289A JP2648202B2 (en) | 1989-02-07 | 1989-02-07 | Vinyl chloride plastisol composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2841289A JP2648202B2 (en) | 1989-02-07 | 1989-02-07 | Vinyl chloride plastisol composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208347A JPH02208347A (en) | 1990-08-17 |
| JP2648202B2 true JP2648202B2 (en) | 1997-08-27 |
Family
ID=12247942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2841289A Expired - Lifetime JP2648202B2 (en) | 1989-02-07 | 1989-02-07 | Vinyl chloride plastisol composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2648202B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4249075B2 (en) * | 2004-04-16 | 2009-04-02 | 新第一塩ビ株式会社 | Vinyl chloride plastisol composition and foam molded article |
| WO2017170156A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ゼオン株式会社 | Spray coating sol, vinyl chloride resin molded body with spray coating layer, manufacturing method for said molded body, and laminate |
| JP2024055490A (en) * | 2022-10-07 | 2024-04-18 | 信越化学工業株式会社 | Resin composition, molded article and method for producing resin composition |
-
1989
- 1989-02-07 JP JP2841289A patent/JP2648202B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02208347A (en) | 1990-08-17 |
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