JP2020153022A - Process paper for synthetic leather, and manufacturing method of synthetic leather - Google Patents
Process paper for synthetic leather, and manufacturing method of synthetic leather Download PDFInfo
- Publication number
- JP2020153022A JP2020153022A JP2019050164A JP2019050164A JP2020153022A JP 2020153022 A JP2020153022 A JP 2020153022A JP 2019050164 A JP2019050164 A JP 2019050164A JP 2019050164 A JP2019050164 A JP 2019050164A JP 2020153022 A JP2020153022 A JP 2020153022A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic leather
- release agent
- agent layer
- process paper
- 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
- 239000002649 leather substitute Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 80
- 230000008569 process Effects 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 107
- 239000000463 material Substances 0.000 claims abstract description 23
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
- 239000004640 Melamine resin Substances 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 14
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 11
- 229920000180 alkyd Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 39
- 239000000945 filler Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 229920003002 synthetic resin Polymers 0.000 claims description 5
- 239000000057 synthetic resin Substances 0.000 claims description 5
- 238000005259 measurement Methods 0.000 abstract description 4
- 229920001296 polysiloxane Polymers 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 79
- 239000000203 mixture Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001187 thermosetting polymer 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、合成皮革用工程紙および合成皮革の製造方法に関する。 The present invention relates to a process paper for synthetic leather and a method for producing synthetic leather.
合成皮革は、紙などの基材上に、剥離剤樹脂組成物からなる剥離剤層を有する工程紙を用いて、剥離剤層上にウレタン樹脂、塩化ビニル樹脂などの合成樹脂を主成分とする塗工液を塗布し乾燥した後、必要に応じてさらにその上に基布を、接着剤を介して貼合し、最終的に合成皮革を工程紙から剥離することにより製造されている。 Synthetic leather uses a process paper having a release agent layer made of a release agent resin composition on a base material such as paper, and has a synthetic resin such as urethane resin or vinyl chloride resin as a main component on the release agent layer. It is manufactured by applying a coating liquid, drying it, and then adhering a base cloth on it, if necessary, with an adhesive, and finally peeling the synthetic leather from the process paper.
工程紙の剥離剤層を構成する剥離剤樹脂組成物として、たとえば、特許文献１には、シリコーン変性アルキド樹脂にアミノ樹脂およびアルキド樹脂を含有させたものが開示されている。
また、特許文献２には、剥離剤樹脂組成物として、メラミン樹脂およびシリコーン変性アルキド樹脂からなるものが開示されている。
As a release agent resin composition constituting the release agent layer of the process paper, for example, Patent Document 1 discloses a silicone-modified alkyd resin containing an amino resin and an alkyd resin.
Further, Patent Document 2 discloses a release agent resin composition composed of a melamine resin and a silicone-modified alkyd resin.
しかしながら、前記特許文献１および特許文献２に開示された剥離材樹脂組成物を用いた合成皮革用工程紙を用いて合成皮革を製造した場合、合成皮革用工程紙の繰り返しの使用により、合成皮革の剥離時に剥離力が増大し、合成皮革の製造効率が低下をしてしまうという課題がある。 However, when synthetic leather is produced using the synthetic leather process paper using the release material resin composition disclosed in Patent Document 1 and Patent Document 2, the synthetic leather is produced by repeatedly using the synthetic leather process paper. There is a problem that the peeling force is increased at the time of peeling, and the production efficiency of synthetic leather is lowered.
本発明の目的は、合成皮革の製造に際して繰り返して使用しても、合成皮革の製造効率が低下することがない合成皮革用工程紙および合成皮革の製造方法を提供することにある。 An object of the present invention is to provide a process paper for synthetic leather and a method for producing synthetic leather, which does not reduce the production efficiency of synthetic leather even if it is repeatedly used in the production of synthetic leather.
本発明の合成皮革用工程紙は、基材と、前記基材上に形成された剥離剤層とを備えた合成皮革用工程紙であって、前記剥離剤層は、シリコーン変性アクリル樹脂とメラミン樹脂、またはシリコーン変性アルキド樹脂とメラミン樹脂のいずれかからなり、ＸＰＳ（X-ray Photoelectron Spectroscopy）により前記剥離剤層の表面を測定したときに、Ｓｉ元素比率が１２％以上である。
この発明によれば、剥離樹脂層の表面のＳｉ元素比率が１２％以上であることにより、剥離剤層と合成皮革用樹脂の剥離力が増大しにくくなるため、合成皮革用工程紙を繰り返して使用しても合成皮革の製造効率が低下することがない。
The process paper for synthetic leather of the present invention is a process paper for synthetic leather provided with a base material and a release agent layer formed on the base material, and the release agent layer is a silicone-modified acrylic resin and melamine. It is composed of either a resin or a silicone-modified alkyd resin and a melamine resin, and when the surface of the release agent layer is measured by XPS (X-ray Photoelectron Spectroscopy), the Si element ratio is 12% or more.
According to the present invention, when the Si element ratio on the surface of the release resin layer is 12% or more, the release force between the release agent layer and the resin for synthetic leather is less likely to increase. Therefore, the process paper for synthetic leather is repeated. Even if it is used, the production efficiency of synthetic leather does not decrease.
本発明では、前記剥離剤層には、さらに不定形粒子からなる充填剤層が０質量％を超え、１２質量％以下含有するのが好ましい。
剥離剤層に充填剤が添加されることにより、表面平滑なエナメル調合成皮革だけでなくマット調、セミマット調など様々な質感の合成皮革を製造することができる。
充填剤の上限を１２質量％以下としたのは、充填剤が１２質量％を超えると、合成皮革の製造工程で充填剤が剥離剤層から脱落しやすくなり、繰り返し使用した場合の合成皮革の質感の変化を招いたり、合成皮革を汚染する可能性がある。
In the present invention, the release agent layer preferably contains a filler layer composed of amorphous particles in an amount of more than 0% by mass and 12% by mass or less.
By adding a filler to the release agent layer, not only enamel-like synthetic leather with a smooth surface but also synthetic leather having various textures such as matte and semi-matte can be produced.
The reason why the upper limit of the filler is 12% by mass or less is that if the filler exceeds 12% by mass, the filler tends to fall off from the release agent layer in the synthetic leather manufacturing process, and the synthetic leather is used repeatedly. It may cause changes in texture and contaminate synthetic leather.
本発明では、前記不定形粒子は、不定形シリカ粒子であるのが好ましい。
この発明によれば、不定形粒子が無機材料から構成されることにより、合成皮革製造中の加熱によっても、変形、溶融することがないので、所望の質感の合成皮革を製造することができる。
In the present invention, the amorphous particles are preferably amorphous silica particles.
According to the present invention, since the amorphous particles are composed of an inorganic material, they are not deformed or melted even by heating during the production of synthetic leather, so that synthetic leather having a desired texture can be produced.
本発明では、前記剥離剤層の膜厚は、３．０μｍ以上、１２μｍ以下であるのが好ましい。
膜厚が３．０μｍ未満では、剥離剤層から露出する充填剤が多くなりすぎることでマット感が強くなってしまい、所望の質感を有する合成皮革を製造することができない。また充填剤が剥離剤層に固定されにくくなり、充填剤が剥離剤層から脱落してしまい、所望の質感を有する合成皮革を製造することができない。
さらに、膜厚が３μｍ未満では、剥離剤層中のシリコーン変性アクリル樹脂またはシリコーン変性アルキド樹脂の絶対量が少なくなり、剥離剤層の表面のＳｉ元素比率が１２％以上を維持するのが困難となる。
In the present invention, the film thickness of the release agent layer is preferably 3.0 μm or more and 12 μm or less.
If the film thickness is less than 3.0 μm, the amount of filler exposed from the release agent layer becomes too large, and the matte feeling becomes strong, so that synthetic leather having a desired texture cannot be produced. In addition, the filler becomes difficult to be fixed to the release agent layer, and the filler falls off from the release agent layer, making it impossible to produce synthetic leather having a desired texture.
Further, if the film thickness is less than 3 μm, the absolute amount of the silicone-modified acrylic resin or the silicone-modified alkyd resin in the release agent layer becomes small, and it is difficult to maintain the Si element ratio on the surface of the release agent layer at 12% or more. Become.
一方、膜厚が１２μｍを超えると、充填剤が剥離剤層中に埋没し、剥離剤層から露出する充填剤が少なくなることで光沢感が強調されてしまい、所望の質感を有する合成皮革を製造することができない。
なお、膜厚との関係では、前記不定形粒子の平均粒子径Ｄ５０は、０．５μｍ以上、５．０μｍ以下であるのが好ましい。
On the other hand, when the film thickness exceeds 12 μm, the filler is buried in the release agent layer, and the amount of the filler exposed from the release agent layer is reduced, so that the glossiness is emphasized, and the synthetic leather having a desired texture is produced. Cannot be manufactured.
In relation to the film thickness, the average particle diameter D50 of the amorphous particles is preferably 0.5 μm or more and 5.0 μm or less.
本発明の合成皮革の製造方法は、前述した合成皮革用工程紙の剥離剤層上に、合成樹脂を含む塗工液を塗布する工程と、塗布された前記塗工液を乾燥して合成皮革を形成する工程と、乾燥後、前記合成皮革用工程紙を前記合成皮革から剥離する工程と、を含む。
この発明によれば、剥離剤層と合成皮革用樹脂の剥離力が増大しにくくなり、合成皮革用工程紙を繰り返し使用して合成皮革を製造できるので、合成皮革の製造効率が低下することがない。
The method for producing synthetic leather of the present invention includes a step of applying a coating liquid containing a synthetic resin on the release agent layer of the above-mentioned process paper for synthetic leather, and a step of drying the applied coating liquid to make synthetic leather. The process includes a step of forming the synthetic leather and a step of peeling the synthetic leather process paper from the synthetic leather after drying.
According to the present invention, the peeling force between the release agent layer and the resin for synthetic leather is less likely to increase, and the synthetic leather can be produced by repeatedly using the process paper for synthetic leather, so that the production efficiency of the synthetic leather can be lowered. Absent.
以下、本発明の実施の形態に係る合成皮革用工程紙は、基材および剥離剤層を備える。
［１］基材
合成皮革用工程紙の基材としては、後述の剥離剤層を支持できるものであれば適宜選択でき、紙基材、樹脂フィルム等が挙げられる。
紙基材としては、たとえば、上質紙、中質紙、グラシン紙、アート紙、コート紙およびキャストコート紙等の紙基材が挙げられ、また、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙も挙げられる。
Hereinafter, the process paper for synthetic leather according to the embodiment of the present invention includes a base material and a release agent layer.
[1] Base material The base material of the process paper for synthetic leather can be appropriately selected as long as it can support the release agent layer described later, and examples thereof include a paper base material and a resin film.
Examples of the paper base material include paper base materials such as high-quality paper, medium-quality paper, glassin paper, art paper, coated paper, and cast-coated paper, and the paper base material is a thermoplastic resin such as polyethylene. There is also a laminated paper in which the above is laminated.
樹脂フィルムとしては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィンからなるフィルムなどが挙げられる。
また、これらは単層であってもよいし、同種または異種の２層以上の多層であってもよい。
基材の厚さは、特に限定されないが、５〜３００μｍであることが好ましく、１０〜２００μｍであることがより好ましい。
これらの基材の中でも、強度および入手が容易である観点から、紙基材が好ましく、キャストコート紙がより好ましい。キャストコート紙を用いることにより、平滑性、耐熱性、バリア性を確保することができる。
キャストコート紙（高光沢紙）としては、たとえば、直接法、リウェット法、凝固法で製造されたものが挙げられるが、市販品としては、日本製紙（株）製のエスプリシリーズ、王子製紙（株）製のミラーコートシリーズ等が挙げられる。
Examples of the resin film include polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, and films made of polyolefins such as polyethylene, polypropylene and polymethylpentene.
Further, these may be a single layer, or may be two or more layers of the same type or different types.
The thickness of the base material is not particularly limited, but is preferably 5 to 300 μm, and more preferably 10 to 200 μm.
Among these base materials, a paper base material is preferable, and cast-coated paper is more preferable, from the viewpoint of strength and easy availability. By using cast coated paper, smoothness, heat resistance, and barrier properties can be ensured.
Examples of cast-coated paper (high-gloss paper) include those manufactured by the direct method, the rewet method, and the coagulation method, but commercially available products include the Esprit series manufactured by Nippon Paper Co., Ltd. and Oji Paper Co., Ltd. ) Mirror coat series and the like.
［２］剥離剤層
剥離剤層は、剥離剤組成物から構成される。剥離剤組成物は、シリコーン変性アクリル樹脂とメラミン樹脂、またはシリコーン変性アルキド樹脂とメラミン樹脂のいずれかから構成される。
[2] Release agent layer The release agent layer is composed of a release agent composition. The release agent composition is composed of either a silicone-modified acrylic resin and a melamine resin, or a silicone-modified alkyd resin and a melamine resin.
剥離剤組成物としては、シリコーン変性アクリル樹脂とメラミン樹脂の混合液を使用することができ、たとえば信越化学工業社製X-62-9088、KS-892、日立化成社製TA31-291Fなどを好適に用いることができる。
また、剥離剤組成物としては、シリコーン変性アルキド樹脂とメラミン樹脂の混合液を使用することができ、たとえば信越化学工業社製X-62-9094、X-62-9095、日立化成社製、TA31-209E、TF-309などを好適に用いることができる。
As the release agent composition, a mixed solution of a silicone-modified acrylic resin and a melamine resin can be used, and for example, X-62-9088 and KS-892 manufactured by Shin-Etsu Chemical Co., Ltd. and TA31-291F manufactured by Hitachi Chemical Co., Ltd. are suitable. Can be used for.
Further, as the release agent composition, a mixed solution of a silicone-modified alkyd resin and a melamine resin can be used, for example, X-62-9094, X-62-9095 manufactured by Shin-Etsu Chemical Co., Ltd., TA31 manufactured by Hitachi Chemical Co., Ltd. -209E, TF-309 and the like can be preferably used.
これらのようなシリコーン変性された樹脂を採用することにより、合成皮革を繰り返し製膜しても変性成分が剥離剤層表面にとどまるため剥離性が維持できる。
また、剥離剤組成物の硬化剤成分としてメラミン樹脂を用いることから、剥離剤層が硬化し、剥離性が向上する。
By adopting a silicone-modified resin such as these, even if the synthetic leather is repeatedly formed into a film, the modified component remains on the surface of the release agent layer, so that the release property can be maintained.
Further, since the melamine resin is used as the curing agent component of the release agent composition, the release agent layer is cured and the release property is improved.
剥離剤層は、ＸＰＳ（X-ray Photoelectron Spectroscopy）により前記剥離剤層の表面を測定したときに、Ｓｉ元素比率が１２％以上である。
剥離剤層の表面のＳｉ元素比率が１２％以上であれば、１０回使用後の剥離剤層の表面のＳｉ元素比率を１０％以上に維持することができるため、剥離力が増加することなく、
合成皮革の製造効率が低下することもない。
The release agent layer has a Si element ratio of 12% or more when the surface of the release agent layer is measured by XPS (X-ray Photoelectron Spectroscopy).
If the Si element ratio on the surface of the release agent layer is 12% or more, the Si element ratio on the surface of the release agent layer after 10 times of use can be maintained at 10% or more, so that the release force does not increase. ,
The production efficiency of synthetic leather does not decrease.
剥離剤層の表面のＳｉ元素比率を１２％以上とするには、基材上に剥離剤組成物を塗布した後、初期の乾燥工程を、通常の剥離剤層の乾燥条件よりも緩やかな条件で行うことにより、シリコーンを含む成分を剥離剤層の表面に偏析させる方法が考えられる。 In order to make the Si element ratio on the surface of the release agent layer 12% or more, after applying the release agent composition on the substrate, the initial drying step is performed under conditions that are more lenient than the normal drying conditions of the release agent layer. A method of segregating the component containing silicone on the surface of the release agent layer can be considered.
合成皮革用工程紙において、硬化後の剥離剤層の膜厚は、特に限定されないが、３μｍ以上、１２μｍ以下が好ましく、３μｍ以上、８μｍ以下がより好ましい。
後述する充填剤との関係もあるが、剥離剤層の膜厚が３μｍ未満であると、剥離剤組成物中のシリコーン変性された樹脂の配合量によっては、剥離剤の表面に偏析するシリコーン変性された樹脂の絶対量が少なくなり、剥離剤層の表面のＳｉ元素化率が１２％未満となる。
膜厚の上限については、特に制限はないが、材料コストの関係、後述する充填剤の剥離剤層の表面への露出状態を考えれば、１２μｍ以下とするのが好ましい。
In the process paper for synthetic leather, the film thickness of the release agent layer after curing is not particularly limited, but is preferably 3 μm or more and 12 μm or less, and more preferably 3 μm or more and 8 μm or less.
Although it is related to the filler described later, if the thickness of the release agent layer is less than 3 μm, the silicone modification segregates on the surface of the release agent depending on the blending amount of the silicone-modified resin in the release agent composition. The absolute amount of the resin is reduced, and the Si elementization rate on the surface of the release agent layer is less than 12%.
The upper limit of the film thickness is not particularly limited, but is preferably 12 μm or less in consideration of the material cost and the exposed state of the filler layer of the filler to the surface, which will be described later.
［３］充填剤
剥離剤組成物には、さらに充填剤を添加してもよい。充填剤としては、不定形のシリカ、アルミナ、酸化チタン、酸化亜鉛、炭酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、カオリン、タルク、クレー等が挙げられ、耐熱性の観点から、不定形シリカ粒子、不定形アルミナ粒子が好ましく、経済的な観点から 不定形シリカを採用することがより好ましい。
また、これらの充填剤は分散性を向上させやすくなることや、剥離剤組成物を構成する剥離主剤との反応性が付与できるようになることを目的として、粒子表面が有機基や官能基などで修飾されていてもよい。
[3] Filler A filler may be further added to the release agent composition. Examples of the filler include amorphous silica, alumina, titanium oxide, zinc oxide, calcium carbonate, magnesium hydroxide, aluminum hydroxide, kaolin, talc, clay, etc. From the viewpoint of heat resistance, amorphous silica particles, Amorphous alumina particles are preferable, and it is more preferable to use amorphous silica from an economical point of view.
Further, these fillers have an organic group, a functional group, or the like on the particle surface for the purpose of easily improving the dispersibility and imparting reactivity with the release main agent constituting the release agent composition. It may be modified with.
剥離剤組成物中に充填剤が添加される場合は、充填剤が０質量％を超え、１２質量％未満の不定形粒子からなる充填剤が添加されていることが好ましい。充填剤の配合比率は、１質量％を超え、１０質量％未満がより好ましい。この範囲とすることで剥離剤層に合成皮革用の樹脂の剥離性を確保しつつ、剥離剤層の耐屈曲性も確保できる所望の鏡面光沢度を有し、かつ適度な剥離力を得ることができる。 When a filler is added to the release agent composition, it is preferable that the filler is composed of more than 0% by mass and less than 12% by mass of amorphous particles. The blending ratio of the filler is more preferably more than 1% by mass and less than 10% by mass. Within this range, the release agent layer has a desired mirror glossiness that can ensure the release property of the resin for synthetic leather and the bending resistance of the release agent layer, and an appropriate release force can be obtained. Can be done.
不定形粒子の平均粒子径Ｄ５０は、０．５μｍ以上、５．０μｍ以下であるのが好ましい。平均粒子径Ｄ５０がこの下限値より小さくなると、充填剤が剥離剤層から露出しにくくなることで光沢感が強くなってしまう恐れがある。また、平均粒子径Ｄ５０がこの上限値より大きくなると、充填剤が剥離剤層から露出しすぎることでマット感が強くなってしまう恐れがある。なお、平均粒子径Ｄ５０は、充填剤が配合された剥離剤組成物を計測対象として、レーザー回折式粒度分布計により測定することができる。 The average particle size D50 of the amorphous particles is preferably 0.5 μm or more and 5.0 μm or less. If the average particle size D50 is smaller than this lower limit, the filler is less likely to be exposed from the release agent layer, which may increase the glossiness. Further, when the average particle size D50 is larger than this upper limit value, the filler may be excessively exposed from the release agent layer, and the matte feeling may be strengthened. The average particle size D50 can be measured by a laser diffraction type particle size distribution meter with a release agent composition containing a filler as a measurement target.
充填剤に用いる不定形粒子は、シリカ、アルミナ等の原材料の塊状体を破砕、粉砕した状態のものであってもよく、沈降法やゲル法などの湿式法による一次粒子の二次凝集により形成されたものであってもよい。
充填剤の比表面積は、１０ｍ２／ｇ以上、好ましくは２０ｍ２／ｇ以上１０００ｍ２／ｇ以下、より好ましくは５０ｍ２／ｇ以上５００ｍ２／ｇ以下であるのが好ましい。
The amorphous particles used for the filler may be in a state where agglomerates of raw materials such as silica and alumina are crushed and crushed, and are formed by secondary aggregation of primary particles by a wet method such as a precipitation method or a gel method. It may be the one that has been done.
The specific surface area of the filler is preferably 10 m 2 / g or more, preferably 20 m 2 / g or more and 1000 m 2 / g or less, and more preferably 50 m 2 / g or more and 500 m 2 / g or less.
剥離剤組成物は、有機溶剤を含む溶液や水を分散媒とする分散液の形態で用いることが好ましい。
有機溶剤としては、たとえば、トルエン、キシレン、ヘキサン、ヘプタン、メタノール、エタノール、イソプロパノール、イソブタノール、ｎ−ブタノール、アセトン、メチルエチルケトン、テトラヒドロフラン等が挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
剥離剤組成物の溶液の不揮発分濃度は、塗工適性および乾燥性の観点より、５質量％以上、６０質量％以下が好ましく、１０質量％以上、５０質量％以下がより好ましく、２０質量％以上、４０質量％以下がさらに好ましい。
The release agent composition is preferably used in the form of a solution containing an organic solvent or a dispersion liquid using water as a dispersion medium.
Examples of the organic solvent include toluene, xylene, hexane, heptane, methanol, ethanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like. These may be used alone or in combination of two or more.
The non-volatile content concentration of the solution of the release agent composition is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and 20% by mass, from the viewpoint of coating suitability and dryness. As mentioned above, 40% by mass or less is more preferable.
［４］合成皮革用工程紙の製造方法
合成皮革用工程紙は、基材と、該基材上に形成された剥離剤層を有する。合成皮革用工程紙の製造方法は、剥離剤層を構成する剥離剤組成物に、必要に応じて充填剤を添加して混合する。
次に、剥離剤組成物を基材上に塗布した後、加熱して有機溶剤を蒸発させて塗膜を形成して剥離剤層を得る。
塗布方法としては、たとえば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ロールナイフコート法、ブレードコート法、ダイコート法、グラビアコート法等が挙げられる。
[4] Method for Producing Process Paper for Synthetic Leather The process paper for synthetic leather has a base material and a release agent layer formed on the base material. In the method for producing process paper for synthetic leather, a filler is added and mixed with the release agent composition constituting the release agent layer, if necessary.
Next, after the release agent composition is applied onto the substrate, it is heated to evaporate the organic solvent to form a coating film to obtain a release agent layer.
Examples of the coating method include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a roll knife coating method, a blade coating method, a die coating method, and a gravure coating method.
前記剥離剤組成物溶液を用いる場合には、該溶液を基材上に塗布して塗膜を形成し、該塗膜を乾燥させるとともに熱硬化させることが好ましい。 When the release agent composition solution is used, it is preferable that the solution is applied onto a substrate to form a coating film, and the coating film is dried and thermoset.
前記剥離剤組成物溶液の乾燥工程は、初期乾燥工程およびその直後の後乾燥工程の２工程以上の工程数で、段階的に乾燥して合成皮革用工程紙を得る。初期乾燥工程は後乾燥工程よりも緩やかな条件で乾燥を行う。初期乾燥工程で、シリコーン変性アクリル樹脂が剥離剤組成物中の気液界面へ向かって偏析し、後乾燥工程で、塗膜中の残留溶剤を完全に乾燥除去するとともに、剥離剤組成物の熱硬化が行われる。初期乾燥工程で偏析したシリコーン変性アクリル樹脂は後乾燥工程の熱硬化で固定され、剥離剤層表面のＳｉ元素比率が高い状態が維持される。初期乾燥工程が行われずに後乾燥工程のみで塗膜の乾燥及び熱硬化を行った場合は、シリコーン変性アクリル樹脂の気液界面への偏析が不十分なまま固定されるため、剥離剤層表面のＳｉ元素比率が低めとなる。 The drying step of the release agent composition solution is a number of steps of two or more steps, that is, an initial drying step and a post-drying step immediately after that, and the process paper for synthetic leather is obtained by stepwise drying. The initial drying step is performed under milder conditions than the post-drying step. In the initial drying step, the silicone-modified acrylic resin segregates toward the gas-liquid interface in the release agent composition, and in the post-drying step, the residual solvent in the coating film is completely dried and removed, and the heat of the release agent composition is removed. Curing is done. The silicone-modified acrylic resin segregated in the initial drying step is fixed by thermosetting in the post-drying step, and the state where the Si element ratio on the surface of the release agent layer is high is maintained. If the coating film is dried and thermoset only in the post-drying step without performing the initial drying step, the silicone-modified acrylic resin is fixed with insufficient segregation to the gas-liquid interface, so that the surface of the release agent layer is fixed. The Si element ratio of is low.
初期乾燥工程での処理温度は、好ましくは常温〜８０℃、より好ましくは常温〜６０℃であり、処理時間は、好ましくは１５秒間〜５分間、より好ましくは２０秒間〜３分間である。塗膜の乾燥を促すように塗膜に直接風を当てることが好ましい。
後乾燥工程での加熱温度は、好ましくは８０〜２５０℃、より好ましくは１００〜２３０℃であり、加熱時間は、好ましくは１５秒間〜５分間、より好ましくは２０秒間〜３分間である。
The treatment temperature in the initial drying step is preferably normal temperature to 80 ° C., more preferably normal temperature to 60 ° C., and the treatment time is preferably 15 seconds to 5 minutes, more preferably 20 seconds to 3 minutes. It is preferable to blow the coating film directly with air so as to promote the drying of the coating film.
The heating temperature in the post-drying step is preferably 80 to 250 ° C., more preferably 100 to 230 ° C., and the heating time is preferably 15 seconds to 5 minutes, more preferably 20 seconds to 3 minutes.
合成皮革用工程紙は、前記の方法に代えて次のような製造方法により製造してもよい。まず、剥離剤層に用いるポリマー材料として熱可塑性の樹脂を使用して、基材上に剥離剤組成物を塗布または溶融押出して剥離剤層を形成する。また、所定の形状を施したエンボスロールを用意し、前記の基材上に剥離剤層を形成した積層体の剥離剤層の表面に対してエンボスロールでプレスし、剥離剤層に所定の凹凸形状を転写することにより、所望の合成皮革用工程紙を製造することができる。 The process paper for synthetic leather may be produced by the following production method instead of the above method. First, a thermoplastic resin is used as the polymer material used for the release agent layer, and the release agent composition is applied or melt-extruded onto the substrate to form the release agent layer. Further, an embossed roll having a predetermined shape is prepared, and the surface of the release agent layer of the laminate in which the release agent layer is formed on the base material is pressed with the emboss roll, and the release agent layer has predetermined irregularities. By transferring the shape, a desired synthetic leather process paper can be produced.
［５］合成皮革の製造方法
合成皮革用工程紙は、合成皮革の製造工程で使用される。
合成皮革用工程紙を用いた合成皮革の製造方法としては、合成皮革用工程紙の剥離剤層上にウレタン樹脂、塩化ビニル樹脂、ポリアミド樹脂等の合成樹脂を主成分とする塗工液を塗布し乾燥して樹脂層を形成した後、必要に応じてさらにその上に基布を、接着剤を介して貼合し、乾燥後、合成皮革を合成皮革用工程紙から剥離することにより製造することができる。
上記合成皮革の製造方法において用いる合成樹脂としては、合成皮革としての風合いや耐久性の観点から、ウレタン樹脂が好ましい。
具体的には、本発明の合成皮革用工程紙の剥離剤層上にウレタン樹脂を塗布し、適宜乾燥してウレタン樹脂層を形成した後、さらに接着剤を介して基布を貼合した後熟成させ、最終的に基布とともにウレタン樹脂層を合成皮革用工程紙から剥離して合成皮革を製造することができる。
[5] Method for manufacturing synthetic leather The process paper for synthetic leather is used in the manufacturing process of synthetic leather.
As a method for producing synthetic leather using synthetic leather process paper, a coating liquid containing a synthetic resin such as urethane resin, vinyl chloride resin, or polyamide resin is applied on the release agent layer of the synthetic leather process paper. After drying to form a resin layer, if necessary, a base cloth is further attached onto the base cloth via an adhesive, and after drying, the synthetic leather is peeled off from the synthetic leather process paper to produce the product. be able to.
As the synthetic resin used in the method for producing synthetic leather, urethane resin is preferable from the viewpoint of texture and durability as synthetic leather.
Specifically, after applying a urethane resin on the release agent layer of the process paper for synthetic leather of the present invention and appropriately drying it to form a urethane resin layer, the base cloth is further bonded via an adhesive. After aging, the urethane resin layer can be peeled off from the synthetic leather process paper together with the base cloth to produce synthetic leather.
合成皮革用工程紙は、合成皮革の樹脂層に対する剥離力が、使用開始初期では３０〜５００ｍＮ／３０ｍｍであることが好ましく、１０回繰り返し使用後の剥離力が１０００ｍＮ／３０ｍｍ以下であるのが好ましい。
上記剥離力がこれら上限値以下であると、合成皮革用工程紙を繰り返し使用した後でも合成皮革からの安定した剥離性能が得られ、また、高い光沢度を有する合成皮革を製造することができる。これら下限値以上であると、樹脂層が剥離剤層から不意に剥がれることを防止することができる。
In the process paper for synthetic leather, the peeling force of the synthetic leather against the resin layer is preferably 30 to 500 mN / 30 mm at the initial stage of use, and the peeling force after repeated use 10 times is preferably 1000 mN / 30 mm or less. ..
When the peeling force is not more than these upper limit values, stable peeling performance from synthetic leather can be obtained even after repeated use of synthetic leather process paper, and synthetic leather having high glossiness can be manufactured. .. When it is at least these lower limit values, it is possible to prevent the resin layer from being unexpectedly peeled from the release agent layer.
以下、本発明の実施例について説明する。なお、本発明は、実施例に限定されるものではない。
［１］実施例
［実施例１］
シリコーン変性アクリル樹脂およびメラミン樹脂（信越化学工業社製 X-62-9088）を主剤とし、不定形シリカ（富士シリシア化学社製 サイシリア420）を樹脂固形分に対して３．３質量％となるように添加した溶液を、基材（日本製紙社製 エスプリコート E(UT)SW）に塗布し、初期乾燥工程およびその直後に後乾燥工程の２工程で乾燥して、剥離剤層の膜厚が７μｍの合成皮革用工程紙を得た。
Hereinafter, examples of the present invention will be described. The present invention is not limited to the examples.
[1] Example [Example 1]
The main component is silicone-modified acrylic resin and melamine resin (X-62-9088 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and amorphous silica (Cycilia 420 manufactured by Fuji Silysia Chemical Ltd.) is adjusted to 3.3% by mass with respect to the resin solid content. The solution added to is applied to the base material (Espricoat E (UT) SW manufactured by Nippon Paper Co., Ltd.) and dried in two steps, an initial drying step and immediately after that, a post-drying step to increase the thickness of the release agent layer. A process paper for synthetic leather of 7 μm was obtained.
初期乾燥工程の条件として、ハンドドライヤー（Panasonic社製、品名：ionity（品番：EH5215P））を剥離剤の塗布面に対して３０ｃｍの位置に配置し、冷風モードで５秒間塗布面を曝した。
また、後乾燥工程の条件として、防爆密閉型乾燥機（エスペック社製、品名：防爆ベントつき恒温器SPH-201）により２００℃、３０秒間で、初期乾燥工程後の塗布シートを静置した。
As a condition of the initial drying step, a hand dryer (manufactured by Panasonic, product name: ionity (product number: EH5215P)) was placed at a position 30 cm with respect to the coating surface of the release agent, and the coating surface was exposed for 5 seconds in the cold air mode.
In addition, as a condition of the post-drying step, the coating sheet after the initial drying step was allowed to stand at 200 ° C. for 30 seconds by an explosion-proof sealed dryer (manufactured by ESPEC, product name: incubator SPH-201 with an explosion-proof vent).
［実施例２］
実施例１の主剤をシリコーン変性アクリル樹脂およびメラミン樹脂（信越化学工業社製 KS-892）に変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
［実施例３］
実施例１の主剤をシリコーン変性アクリル樹脂およびメラミン樹脂（日立化成社製 TA31-291F）に変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
［実施例４］
実施例１の主剤をシリコーン変性アルキド樹脂およびメラミン樹脂（日立化成社製 TF-309）に変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
[Example 2]
The main agent of Example 1 was changed to a silicone-modified acrylic resin and a melamine resin (KS-892 manufactured by Shin-Etsu Chemical Co., Ltd.), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 3]
The main agent of Example 1 was changed to a silicone-modified acrylic resin and a melamine resin (TA31-291F manufactured by Hitachi Chemical Co., Ltd.), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 4]
The main agent of Example 1 was changed to a silicone-modified alkyd resin and a melamine resin (TF-309 manufactured by Hitachi Chemical Co., Ltd.), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［実施例５］
実施例１において、初期乾燥工程の条件を、ハンドドライヤー（実施例１と同じもの）を塗布面に対して３０ｃｍの位置に配置し、温風モード（１２００Ｗ）で５秒間塗布面を曝すことに変更した以外は、実施例１と同様にして合成皮革用工程紙を得た。
［実施例６］
実施例１の不定形シリカを６．６質量％に変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
［実施例７］
実施例１の不定形シリカを１．７質量％に変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
[Example 5]
In Example 1, the condition of the initial drying step was to place a hand dryer (same as in Example 1) at a position 30 cm with respect to the coated surface and expose the coated surface for 5 seconds in warm air mode (1200 W). A process paper for synthetic leather was obtained in the same manner as in Example 1 except that it was changed.
[Example 6]
The amorphous silica of Example 1 was changed to 6.6% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 7]
The amorphous silica of Example 1 was changed to 1.7% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［実施例８］
実施例１の不定形シリカを除去し、実施例１と同様の方法で合成皮革用工程紙を得た。
［実施例９］
実施例２の不定形シリカを除去し、実施例２と同様の方法で合成皮革用工程紙を得た。
［実施例１０］
実施例１の剥離剤層の膜厚を６μｍに変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
［実施例１１］
実施例１の剥離剤層の膜厚を５μｍに変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
[Example 8]
The amorphous silica of Example 1 was removed, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 9]
The amorphous silica of Example 2 was removed, and a process paper for synthetic leather was obtained in the same manner as in Example 2.
[Example 10]
The film thickness of the release agent layer of Example 1 was changed to 6 μm, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 11]
The film thickness of the release agent layer of Example 1 was changed to 5 μm, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［実施例１２］
実施例２の剥離剤層の膜厚を６μｍに変更し、実施例２と同様の方法で合成皮革用工程紙を得た。
［実施例１３］
実施例２の剥離剤層の膜厚を５μｍに変更し、実施例２と同様の方法で合成皮革用工程紙を得た。
［実施例１４］
実施例１において、ゾーンを複数有する乾燥炉を備えた塗工装置を用いて、初期乾燥工程および後乾燥工程を行ったこと以外は、実施例１と同様にして合成皮革用工程紙を得た。なお、塗工装置のライン速度を６０ｍ／ｍｉｎとし、６５℃風速５ｍ／ｓｅｃのゾーンを通過する時間を５秒（初期乾燥工程）、２００℃風速１２ｍ／ｍｉｎのゾーンを通過する時間を２５秒（後乾燥工程）となるようにした。
[Example 12]
The film thickness of the release agent layer of Example 2 was changed to 6 μm, and a process paper for synthetic leather was obtained in the same manner as in Example 2.
[Example 13]
The film thickness of the release agent layer of Example 2 was changed to 5 μm, and a process paper for synthetic leather was obtained in the same manner as in Example 2.
[Example 14]
In Example 1, a process paper for synthetic leather was obtained in the same manner as in Example 1 except that the initial drying step and the post-drying step were performed using a coating device equipped with a drying furnace having a plurality of zones. .. The line speed of the coating device is 60 m / min, the time to pass through the zone of 65 ° C. wind speed of 5 m / sec is 5 seconds (initial drying process), and the time to pass through the zone of 200 ° C. wind speed of 12 m / min is 25 seconds. (Post-drying process).
［２］比較例
［比較例１］
実施例３において、初期乾燥工程を実施例５に同じ温風モードの処理に変更し、実施例３と同様の方法で合成皮革用工程紙を得た。
［比較例２］
実施例４において、初期乾燥工程を実施例５に同じ温風モードの処理に変更し、実施例４と同様の方法で合成皮革用工程紙を得た。
[2] Comparative example [Comparative example 1]
In Example 3, the initial drying step was changed to the same warm air mode treatment as in Example 5, and a process paper for synthetic leather was obtained in the same manner as in Example 3.
[Comparative Example 2]
In Example 4, the initial drying step was changed to the same warm air mode treatment as in Example 5, and a process paper for synthetic leather was obtained in the same manner as in Example 4.
［比較例３］
実施例１の主剤をシリコーン未変性の樹脂（ＤＩＣ社製A-817）に変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
［比較例４］
実施例１の剥離剤層の膜厚を１．５μｍに変更し、実施例１と同様の方法で合成皮革用工程紙を得た。
[Comparative Example 3]
The main agent of Example 1 was changed to a silicone-unmodified resin (A-817 manufactured by DIC Corporation), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Comparative Example 4]
The film thickness of the release agent layer of Example 1 was changed to 1.5 μm, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［３］試験方法
［3-1］剥離力評価
ポリウレタン樹脂溶液（ＤＩＣ社製クリスボン5516S）を合成皮革用工程紙上に塗布し、140℃、２分乾燥し、厚み２５μmのポリウレタン樹脂層を形成した。その後ポリウレタン樹脂層の表面にポリエステル粘着テープ（日東電工社製31Bテープ）を貼合し、２３℃、相対湿度５０％の恒温室内に３０分間静置し、幅３０ｍｍに裁断して試験片とした。引張試験機（エー・アンド・デイ製テンシロン）を用いて、剥離速度１０００ｍｍ／ｍｉｎで１８０°方向に引っ張り、剥離した際の力を測定し、これを初期剥離力とした。
初期剥離力測定後、上記手順通り、ポリウレタン樹脂層の形成、および剥離速度１０００ｍｍ／ｍｉｎで剥離を繰り返し、１０回繰り返し使用後の剥離したときの力を測定し、１０回剥離力とした。
[3] Test method [3-1] Evaluation of peeling force A polyurethane resin solution (Chrisbon 5516S manufactured by DIC Corporation) was applied onto a process paper for synthetic leather and dried at 140 ° C. for 2 minutes to form a polyurethane resin layer having a thickness of 25 μm. .. After that, a polyester adhesive tape (31B tape manufactured by Nitto Denko KK) was attached to the surface of the polyurethane resin layer, left in a constant temperature room at 23 ° C and 50% relative humidity for 30 minutes, and cut into 30 mm width to make a test piece. .. Using a tensile tester (Tensilon manufactured by A & D Co., Ltd.), the force at the time of pulling in the 180 ° direction at a peeling speed of 1000 mm / min was measured, and this was used as the initial peeling force.
After the initial peeling force measurement, the formation of the polyurethane resin layer and the peeling were repeated at a peeling speed of 1000 mm / min according to the above procedure, and the peeling force after repeated use 10 times was measured and used as the peeling force 10 times.
［3-2］Ｓｉ元素比率の測定
ＸＰＳ（X-ray Photoelectron Spectroscopy：Ｘ線光電子分光分析）により、剥離剤層の表面のＳｉ元素比率を測定した。
最初の製膜時における剥離剤層の表面のＳｉ元素比率を初期元素比率とし、１０回繰り返し使用後における剥離剤層の表面のＳｉ元素比率を１０回元素比率とした。
なお、ＸＰＳで用いた装置は、島津製作所 ESCA-3400であり、Ｘ線アノード（発生源）にはＭｇを用いた。Ｘ線の出力は加速電圧１０ｋＶ、およびエミッション電流１５ｍＡで測定を行った。なお、Ｓｉの元素比率は、検出元素をＣ、Ｏ、Ｎ、Ｓｉの４元素として、４元素の合計量を１００％とした場合の、Ｓｉが占める比率（％）をＳｉ元素比率とした。
[3-2] Measurement of Si element ratio The Si element ratio on the surface of the release agent layer was measured by XPS (X-ray Photoelectron Spectroscopy).
The Si element ratio on the surface of the release agent layer at the time of initial film formation was defined as the initial element ratio, and the Si element ratio on the surface of the release agent layer after repeated use 10 times was defined as the element ratio 10 times.
The device used in XPS was Shimadzu ESCA-3400, and Mg was used as the X-ray anode (source). The X-ray output was measured at an accelerating voltage of 10 kV and an emission current of 15 mA. As for the element ratio of Si, the ratio (%) occupied by Si was defined as the Si element ratio when the detected elements were the four elements C, O, N, and Si and the total amount of the four elements was 100%.
［４］試験結果
試験結果を表１に示す。
[4] Test results Table 1 shows the test results.
実施例１から実施例１４を見る限り、Ｓｉの初期元素比率が１２％以上であれば、１０回剥離力を１０００ｍＮ／３０ｍｍ未満に抑えることができ、合成皮革用工程紙を１０回繰り返し使用しても、剥離性が低下することがないことを確認することができた。
一方、比較例１および比較例２では、初期乾燥速度が速すぎるため、剥離剤層の表面にシリコーン変性アクリル樹脂が偏析せず、剥離剤層の表面のＳｉ元素比率が１２％未満となってしまい、１０回繰り返し使用後の剥離力が増大し、合成皮革の製造効率が低下してしまうことが確認された。
また、比較例４では、剥離剤層の膜厚が薄すぎて、結果として剥離剤層中のシリコーン変性アクリル樹脂の絶対量が少なくなってしまい、剥離剤層の表面のＳｉ元素比率を１２％以上とすることができなかった。
As far as Examples 1 to 14 are seen, if the initial element ratio of Si is 12% or more, the peeling force can be suppressed to less than 1000 mN / 30 mm 10 times, and the synthetic leather process paper is repeatedly used 10 times. However, it was confirmed that the peelability did not decrease.
On the other hand, in Comparative Example 1 and Comparative Example 2, since the initial drying rate was too fast, the silicone-modified acrylic resin was not segregated on the surface of the release agent layer, and the Si element ratio on the surface of the release agent layer was less than 12%. Therefore, it was confirmed that the peeling force after repeated use 10 times increases and the production efficiency of synthetic leather decreases.
Further, in Comparative Example 4, the film thickness of the release agent layer is too thin, and as a result, the absolute amount of the silicone-modified acrylic resin in the release agent layer becomes small, and the Si element ratio on the surface of the release agent layer is 12%. I couldn't do more.
Claims (6)
前記剥離剤層は、シリコーン変性アクリル樹脂とメラミン樹脂、またはシリコーン変性アルキド樹脂とメラミン樹脂のいずれかからなり、ＸＰＳ（X-ray Photoelectron Spectroscopy）により前記剥離剤層の表面を測定したときに、Ｓｉ元素比率が１２％以上である合成皮革用工程紙。 A process paper for synthetic leather provided with a base material and a release agent layer formed on the base material.
The release agent layer is composed of either a silicone-modified acrylic resin and a melamine resin, or a silicone-modified alkyd resin and a melamine resin, and when the surface of the release agent layer is measured by XPS (X-ray Photoelectron Spectroscopy), Si Process paper for synthetic leather with an element ratio of 12% or more.
前記剥離剤層には、さらに不定形粒子からなる充填剤が０質量％を超え、１２質量％以下含有する合成皮革用工程紙。 In the process paper for synthetic leather according to claim 1.
A process paper for synthetic leather in which the release agent layer further contains a filler composed of amorphous particles in an amount of more than 0% by mass and 12% by mass or less.
前記不定形粒子の平均粒子径Ｄ５０は、０．５μｍ以上、５．０μｍ以下である合成皮革用工程紙。 In the process paper for synthetic leather according to claim 2.
A process paper for synthetic leather in which the average particle size D50 of the amorphous particles is 0.5 μm or more and 5.0 μm or less.
前記不定形粒子は、不定形シリカ粒子である合成皮革用工程紙。 In the synthetic leather process paper according to claim 2 or 3.
The amorphous particles are process papers for synthetic leather which are amorphous silica particles.
前記剥離剤層の膜厚は、３．０μｍ以上、１２μｍ以下である合成皮革用工程紙。 In the process paper for synthetic leather according to any one of claims 1 to 4.
A process paper for synthetic leather having a film thickness of the release agent layer of 3.0 μm or more and 12 μm or less.
塗布された前記塗工液を乾燥して合成皮革を形成する工程と、
乾燥後、前記合成皮革用工程紙を前記合成皮革から剥離する工程と、
を含む合成皮革の製造方法。 A step of applying a coating liquid containing a synthetic resin on a release agent layer of the process paper for synthetic leather according to any one of claims 1 to 5.
The process of drying the applied coating liquid to form synthetic leather, and
After drying, the step of peeling the synthetic leather process paper from the synthetic leather and
Manufacturing method of synthetic leather including.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019050164A JP2020153022A (en) | 2019-03-18 | 2019-03-18 | Process paper for synthetic leather, and manufacturing method of synthetic leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019050164A JP2020153022A (en) | 2019-03-18 | 2019-03-18 | Process paper for synthetic leather, and manufacturing method of synthetic leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2020153022A true JP2020153022A (en) | 2020-09-24 |
Family
ID=72558022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019050164A Pending JP2020153022A (en) | 2019-03-18 | 2019-03-18 | Process paper for synthetic leather, and manufacturing method of synthetic leather |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2020153022A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022138485A1 (en) * | 2020-12-23 | 2022-06-30 | 東洋紡株式会社 | Method for producing mold release film for resin sheet molding |
| WO2022202383A1 (en) * | 2021-03-26 | 2022-09-29 | リンテック株式会社 | Release sheet |
| WO2024037055A1 (en) * | 2022-08-18 | 2024-02-22 | 中广核达胜加速器技术有限公司 | Leather release paper production apparatus and leather release paper production method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003066327A1 (en) * | 2002-02-04 | 2003-08-14 | Asahi Kasei Kabushiki Kaisha | Releasing material and release agent |
| JP2017177434A (en) * | 2016-03-29 | 2017-10-05 | リンテック株式会社 | Process paper for producing synthetic leather |
-
2019
- 2019-03-18 JP JP2019050164A patent/JP2020153022A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003066327A1 (en) * | 2002-02-04 | 2003-08-14 | Asahi Kasei Kabushiki Kaisha | Releasing material and release agent |
| JP2017177434A (en) * | 2016-03-29 | 2017-10-05 | リンテック株式会社 | Process paper for producing synthetic leather |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022138485A1 (en) * | 2020-12-23 | 2022-06-30 | 東洋紡株式会社 | Method for producing mold release film for resin sheet molding |
| CN116635160A (en) * | 2020-12-23 | 2023-08-22 | 东洋纺株式会社 | Method for producing release film for molding resin sheet |
| WO2022202383A1 (en) * | 2021-03-26 | 2022-09-29 | リンテック株式会社 | Release sheet |
| WO2024037055A1 (en) * | 2022-08-18 | 2024-02-22 | 中广核达胜加速器技术有限公司 | Leather release paper production apparatus and leather release paper production method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2020153022A (en) | Process paper for synthetic leather, and manufacturing method of synthetic leather | |
| JP4217315B2 (en) | Release coating composition, release product comprising the release coating composition, and method for producing the release product | |
| CN110067157B (en) | Release paper for synthetic leather and method for producing synthetic leather | |
| JP2004115972A (en) | Composition for mat layer formation and mold release sheet using the same | |
| JP5837411B2 (en) | Polyester film for in-mold transfer | |
| CN104968493B (en) | Metallize oriented polypropylene coated film | |
| JP5833427B2 (en) | Laminated polyester film for transfer | |
| TWI724240B (en) | Release film and production method thereof | |
| JP2020146890A (en) | Process paper for synthetic leather and manufacturing method of process paper for synthetic leather | |
| JP2013129077A (en) | Laminated polyester film for in-mold transfer foil | |
| JP6373774B2 (en) | Base paper for process release paper and method for producing the same | |
| JP2002361815A (en) | Release paper and synthetic leather manufactured using the same | |
| JP4448607B2 (en) | Multilayer resin stretched film | |
| JP4936563B2 (en) | Surface modifier for polymer materials | |
| JP4365549B2 (en) | Easy peelable multilayer resin stretched film | |
| JPH0784648B2 (en) | Metal film transfer sheet base material and metal film transfer sheet | |
| JP7308673B2 (en) | Casting paper for synthetic leather and method for producing synthetic leather | |
| JP4569998B2 (en) | Release paper and synthetic leather produced using it | |
| JP3226639B2 (en) | Release paper and method for producing the same | |
| JP7478005B2 (en) | Process Film | |
| JP2023000178A (en) | Process paper for synthetic leather, method for producing synthetic leather, and synthetic leather | |
| JP2011173372A (en) | In-mold transfer laminate film and in-mold transfer processing member comprising the same | |
| JP2021154539A (en) | Process film | |
| JP7425643B2 (en) | Process film and process film manufacturing method | |
| EP0617748A1 (en) | Lining material, method for coating a material for producing a lining |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220107 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230112 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230131 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230725 |