JP2020146890A - Process paper for synthetic leather and manufacturing method of process paper for synthetic leather - Google Patents
Process paper for synthetic leather and manufacturing method of process paper for synthetic leather Download PDFInfo
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Abstract
Description
本発明は、合成皮革用工程紙および合成皮革用工程紙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 a process paper for 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に記載の剥離剤樹脂組成物を用いた工程紙は、耐屈曲性に乏しく、合成皮革の製造中に繰り返しの使用によって剥離剤層にクラック等が発生する可能性があるという課題がある。 However, the process papers using the release agent resin compositions described in Patent Documents 1 and 2 have poor bending resistance, and cracks and the like occur in the release agent layer due to repeated use during the production of synthetic leather. There is a problem that there is a possibility.
本発明の目的は、耐屈曲性を向上させ、合成皮革の製造中に繰り返しの使用によっても剥離剤層にクラック等が発生する可能性を低減した合成皮革用工程紙および合成皮革用工程紙の製造方法を提供することにある。 An object of the present invention is to use a synthetic leather process paper and a synthetic leather process paper, which have improved bending resistance and reduced the possibility of cracks in the release agent layer even after repeated use during the production of synthetic leather. The purpose is to provide a manufacturing method.
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およびメラミン樹脂からなる剥離主剤が８０質量％以下２０質量％以上と、ガラス転移点が１００℃以下のシリコーン未変性ポリアクリル酸エステル樹脂が２０質量％以上８０質量％以下とからなる。 The synthetic leather process paper of the present invention is a synthetic leather process paper 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. The release main agent made of resin is 80% by mass or less and 20% by mass or more, and the silicone-unmodified polyacrylic acid ester resin having a glass transition point of 100 ° C. or less is 20% by mass or more and 80% by mass or less.
シリコーン未変性ポリアクリル酸エステル樹脂のガラス転移点（Tg）は、２０℃以上、１００℃以下である。シリコーン未変性ポリアクリル酸エステル樹脂のガラス転移温度が２０℃を下回ると、合成皮革との剥離力が大きくなり過ぎてしまい、作業性が悪くなったり、強度の小さい合成皮革の場合は剥離操作で破断してしまう場合がある。また、１００℃を超えると、剥離剤層の硬度が高すぎて繰り返し使用で生じるクラックの発生を低減する効果を期待できない。 The glass transition point (Tg) of the silicone-unmodified polyacrylic acid ester resin is 20 ° C. or higher and 100 ° C. or lower. If the glass transition temperature of the silicone-unmodified polyacrylic acid ester resin falls below 20 ° C, the peeling force from the synthetic leather becomes too large, resulting in poor workability or, in the case of low-strength synthetic leather, the peeling operation is performed. It may break. Further, if the temperature exceeds 100 ° C., the hardness of the release agent layer is too high, and the effect of reducing the occurrence of cracks generated by repeated use cannot be expected.
本発明では、前記剥離層は、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からである。
In the present invention, it is preferable that the release layer further contains a filler 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. This is because it may cause a change in texture or contaminate synthetic leather.
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。
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。
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.
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.
本発明の合成皮革用工程紙の製造方法は、前述の合成皮革用工程紙の製造方法であって、前記剥離主剤に、前記シリコーン未変性ポリアクリル酸エステルを添加して混合する工程と、混合液を前記基材に塗布する工程と、前記基材に塗布された前記混合液を加熱して塗膜を得る工程と、を実施する。
この発明によれば、耐屈曲性が向上した合成皮革用工程紙を製造することができる。
The method for producing a process paper for synthetic leather of the present invention is the above-mentioned method for producing a process paper for synthetic leather, which is mixed with a step of adding and mixing the silicone-unmodified polyacrylic acid ester to the release main agent. A step of applying the liquid to the base material and a step of heating the mixed liquid applied to the base material to obtain a coating film are carried out.
According to the present invention, it is possible to produce a process paper for synthetic leather having improved bending resistance.
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。
The synthetic leather process paper 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およびメラミン樹脂からなる剥離主剤と、ガラス転移点が１００℃以下のシリコーン未変性ポリアクリル酸エステル樹脂とから構成される。
[2] Release agent layer The release agent layer is composed of a release agent composition. The release agent composition is composed of a release main agent composed of a silicone-modified acrylic resin and a melamine resin, and a silicone-unmodified polyacrylic acid ester resin having a glass transition point of 100 ° C. or lower.
剥離主剤としては、シリコーン変性アクリル樹脂および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、日立化成社製TA31-291Fなどを好適に用いることができる。
剥離剤組成物の剥離主剤として、シリコーン変性アクリル樹脂を使用するのは、シリコーン未変性アクリル樹脂との相溶性がよく、剥離剤組成物を基材に塗工する際の塗工性が向上し、剥離剤層表面の粗さ形状を制御しやすくなるためである。
また、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。
剥離主剤の硬化剤成分としてメラミン樹脂を用いることから、剥離剤層が十分に硬化し、剥離性が向上する。
As the peeling main agent, a mixed solution of a silicone-modified acrylic resin and a melamine resin can be used, and for example, X-62-9088 manufactured by Shin-Etsu Chemical Co., Ltd., TA31-291F manufactured by Hitachi Chemical Co., Ltd., and the like can be preferably used.
Using a silicone-modified acrylic resin as the release main agent of the release agent composition has good compatibility with the silicone-unmodified acrylic resin, and improves the coatability when the release agent composition is applied to the substrate. This is because it becomes easier to control the roughness shape of the surface of the release agent layer.
Further, by adopting the silicone-modified resin, 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.
Since the melamine resin is used as the curing agent component of the release main agent, the release agent layer is sufficiently cured and the release property is improved.
シリコーン未変性ポリアクリル酸エステル樹脂は、剥離主剤が８０質量％以下２０質量％以上に対して２０質量％以上８０質量％以下配合される。シリコーン未変性ポリアクリル酸エステル樹脂が２０質量％未満では、剥離剤層の硬度が十分に低減しないので、耐屈曲性に劣る。シリコーン未変性ポリアクリル酸エステル樹脂が８０質量％を超えると、残部の剥離主剤の量が足りなくなり、合成皮革用の樹脂に対する剥離性が低下する。 The silicone-unmodified polyacrylic acid ester resin contains 20% by mass or more and 80% by mass or less of the release main agent with respect to 80% by mass or less and 20% by mass or more. If the silicone-unmodified polyacrylic acid ester resin is less than 20% by mass, the hardness of the release agent layer is not sufficiently reduced, so that the bending resistance is inferior. If the amount of the silicone-unmodified polyacrylic acid ester resin exceeds 80% by mass, the amount of the remaining peeling main agent becomes insufficient, and the peelability to the resin for synthetic leather is lowered.
剥離剤層を柔軟化するためにシリコーン未変性アクリル樹脂を用いる理由としては、共重合成分により高温から低温まで幅広いガラス転移点をもつ樹脂を得られることから、目的とする柔軟性を示す剥離剤層を得やすいうえに、さまざまな官能基をもたせることができるので、剥離剤層に特異な機能を付加できる可能性があるからである。
シリコーン未変性ポリアクリル酸エステル樹脂としては、ガラス転移点（Ｔｇ）が１００℃以下のものを用いることができ、たとえばＤＩＣ社製A-811-BE（Tg=20℃）、WMU-504(Tg=60℃)、A-817（Tg=95℃）などを好適に用いることができる。
The reason for using a silicone-unmodified acrylic resin to soften the release agent layer is that a resin having a wide glass transition point from high temperature to low temperature can be obtained by the copolymerization component, so that the release agent exhibiting the desired flexibility. This is because it is easy to obtain a layer and it is possible to have various functional groups, so that it is possible to add a unique function to the release agent layer.
As the silicone-unmodified polyacrylic acid ester resin, a resin having a glass transition point (Tg) of 100 ° C. or lower can be used, for example, A-811-BE (Tg = 20 ° C.) manufactured by DIC Corporation, WMU-504 (Tg). = 60 ° C), A-817 (Tg = 95 ° C) and the like can be preferably used.
［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.
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 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、剥離主剤に、シリコーン未変性ポリアクリル酸エステルおよび有機溶剤を添加して混合する。なお、充填剤をさらに添加する場合には、この際に同時に行う。
次に、混合液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。
[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 silicone-unmodified polyacrylic acid ester and an organic solvent are added and mixed with a release main agent. When further filler is added, it is carried out at the same time.
Next, after the mixed solution is applied onto the substrate, it is heated to evaporate the organic solvent to form a coating film to obtain a release agent layer.
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。 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、該塗膜を加熱して乾燥させることが好ましい。
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。
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。
When the release agent composition solution is used, it is preferable to apply the solution on a substrate to form a coating film, and heat and dry the coating film.
The heating temperature 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.
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.
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、剥離主剤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 a polymer material used as a release main agent, and a release agent composition is applied or melt-extruded onto a substrate to form a 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］合成皮革用工程紙の使用方法
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、該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て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] How to use the process paper for 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 as a main component is applied on the release agent layer of the synthetic leather process paper. After applying and 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. can do.
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, a urethane resin is applied onto the release agent layer of the synthetic leather process paper of the present invention and appropriately dried to form a urethane resin layer, and then 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、３０〜３０００ｍＮ／３０ｍｍであることが好ましく、５０〜２０００ｍＮ／３０ｍｍであることがより好ましく、６０〜１０００ｍＮ／３０ｍｍであることがさらに好ましく、７０〜５００ｍＮ／３０ｍｍであることがよりさらに好ましく、９０〜２００ｍＮ／３０ｍｍであることがよりさらに好ましい。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。 The process paper for synthetic leather preferably has a peeling force of the synthetic leather with respect to the resin layer of 30 to 3000 mN / 30 mm, more preferably 50 to 2000 mN / 30 mm, and further preferably 60 to 1000 mN / 30 mm. It is more preferably 70 to 500 mN / 30 mm, and even more preferably 90 to 200 mN / 30 mm. 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）を剥離主剤６６．７質量%に対し、シリコーン未変性ポリアクリル酸エステル樹脂（ＤＩＣ社製 A-811-BE(Tg=20℃)）を３０質量％、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）に膜厚７μｍとなるように塗布し、２００℃、１ｍｉｎ加熱し、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]
Silicone-modified acrylic resin and melamine resin (X-62-9088 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) are stripped from 66.7% by mass of the main agent, and silicone-unmodified polyacrylic acid ester resin (A-811-BE (Tg =) manufactured by DIC). 20 ° C))) was added to 30% by mass, and amorphous silica (Cycilia 420 manufactured by Fuji Silysia Chemical Ltd.) was added so as to be 3.3% by mass based on the resin solid content, and the base material (Esprit manufactured by Nippon Paper Co., Ltd.) was added. It was applied to Coat E (UT) SW) to a thickness of 7 μm and heated at 200 ° C. for 1 min to obtain a process paper for synthetic leather.
［実施例２］
実施例１の剥離主剤を４６．７質量％、かつ、シリコーン未変性アクリル酸ポリエステル樹脂の添加量を５０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３］
実施例１の剥離主剤を２６．７質量％、かつ、シリコーン未変性アクリル酸ポリエステル樹脂の添加量を７０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 2]
The release main agent of Example 1 was changed to 46.7% by mass, and the addition amount of the silicone-unmodified polyester acrylate resin was changed to 50% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 3]
The release main agent of Example 1 was changed to 26.7% by mass, and the addition amount of the silicone-unmodified polyester acrylate resin was changed to 70% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［実施例４］
実施例１の剥離主剤を６６．７質量％、かつ、不定形シリカの添加量を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５］
実施例１の剥離主剤を７０質量％、かつ、不定形シリカを未添加として、実施例１と同様の方法で合成皮革用工程紙を得た。
[Example 4]
The release base material of Example 1 was changed to 66.7% by mass, and the amount of amorphous silica added 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 5]
A process paper for synthetic leather was obtained in the same manner as in Example 1 by using 70% by mass of the peeling main agent of Example 1 and no addition of amorphous silica.
［実施例６］
実施例１の剥離主剤を変更し（信越化学工業社製 TA31-291F）、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のシリコーン未変性ポリアクリル酸エステル樹脂を変更し（ＤＩＣ社製 WMU-504(Tg=60℃)）、実施例１と同様の方法で合成皮革用工程紙を得た。
[Example 6]
The peeling main agent of Example 1 was changed (TA31-291F 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 7]
The silicone-unmodified polyacrylic acid ester resin of Example 1 was changed (WMU-504 (Tg = 60 ° C.) manufactured by DIC Corporation), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［実施例８］
実施例７の剥離主剤を４６．７質量％、かつ、シリコーン未変性ポリアクリル酸エステル樹脂の添加量を５０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９］
実施例７の剥離主剤を２６．７質量％、かつ、シリコーン未変性ポリアクリル酸エステル樹脂の添加量を７０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 8]
The release main agent of Example 7 was changed to 46.7% by mass, and the amount of the silicone-unmodified polyacrylic acid ester resin added was changed to 50% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1. ..
[Example 9]
The release main agent of Example 7 was changed to 26.7% by mass, and the amount of the silicone-unmodified polyacrylic acid ester resin added was changed to 70% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1. ..
［実施例１０］
実施例１のシリコーン未変性ポリアクリル酸エステル樹脂を変更し（ＤＩＣ社製 A-817(Tg=95℃)）、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１０の剥離主剤を４６．７質量％、かつ、添加量を５０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１２］
実施例１０の剥離主剤を２６．７質量％、かつ、添加量を７０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 10]
The silicone-unmodified polyacrylic acid ester resin of Example 1 was changed (A-817 (Tg = 95 ° C.) manufactured by DIC Corporation), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 11]
The release main agent of Example 10 was changed to 46.7% by mass and the addition amount was changed to 50% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Example 12]
The release main agent of Example 10 was changed to 26.7% by mass and the addition amount was changed to 70% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1.
［２］比較例
［比較例１］
実施例１の剥離主剤を９６．７質量％、かつ、にシリコーン未変性ポリアクリル酸エステル樹脂を添加しないで、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２］
実施例６の剥離主剤を９６．７質量％、かつ、にシリコーン未変性ポリアクリル酸エステル樹脂を添加しないで、実施例６と同様の方法で合成皮革用工程紙を得た。
[2] Comparative example [Comparative example 1]
A process paper for synthetic leather was obtained in the same manner as in Example 1 by adding 96.7% by mass of the release main agent of Example 1 and no silicone-unmodified polyacrylic acid ester resin.
[Comparative Example 2]
A process paper for synthetic leather was obtained in the same manner as in Example 6 without adding a silicone-unmodified polyacrylic acid ester resin to 96.7% by mass of the peeling main agent of Example 6.
［比較例３］
実施例１のシリコーン未変性ポリアクリル酸エステル樹脂を変更し（三井化学社製 Q828(Tg=135℃)）、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の剥離主剤を８６．７質量％、かつ、シリコーン未変性ポリアクリル酸エステル樹脂の添加量を１０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。
[Comparative Example 3]
The silicone-unmodified polyacrylic acid ester resin of Example 1 was changed (Q828 (Tg = 135 ° C.) manufactured by Mitsui Chemicals, Inc.), and a process paper for synthetic leather was obtained in the same manner as in Example 1.
[Comparative Example 4]
The release main agent of Example 1 was changed to 86.7% by mass, and the amount of the silicone-unmodified polyacrylic acid ester resin added was changed to 10% by mass, and a process paper for synthetic leather was obtained in the same manner as in Example 1. ..
［３］試験方法
JIS K 5600-1 円筒形マンドレル法により、合成皮革用工程紙の耐屈曲性の評価を行った。具体的には、幅３０ｍｍ×長さ１３０ｍｍの試験片を２３℃、５０％ＲＨ条件下で１日調湿した後、それぞれの試験片を、剥離剤層を外側にして、マンドレル（丸棒）に沿うように蝶番状治具により折り曲げる。折り曲げ後の剥離剤層にクラックが入る最大のマンドレルの直径を試験片の耐屈曲性の評価値とした。なお、マンドレルの直径は、２、３、４、５、６、１０、１２、１６、２０、２５、３２ｍｍのものを準備した。
[3] Test method
The bending resistance of process paper for synthetic leather was evaluated by the JIS K 5600-1 cylindrical mandrel method. Specifically, after adjusting the humidity of a test piece having a width of 30 mm and a length of 130 mm for one day under the conditions of 23 ° C. and 50% RH, each test piece is placed on a mandrel (round bar) with the release agent layer on the outside. Bend with a hinge-shaped jig along the above. The diameter of the maximum mandrel at which the release agent layer after bending was cracked was used as the evaluation value of the bending resistance of the test piece. The diameter of the mandrel was 2, 3, 4, 5, 6, 10, 12, 16, 20, 25, and 32 mm.
［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１２の耐屈曲性を見る限り、６ｍｍ以下の耐屈曲性を有し、耐屈曲性に優れ、合成皮革用工程紙の繰り返し使用によっても、剥離剤層にクラック等が発生する可能性が少ないことが確認された。
一方、比較例１、比較例２のようにシリコーン未変性ポリアクリル酸エステル樹脂を添加しない場合や、比較例４のように添加量が少ない場合は、耐屈曲性が著しく低下することが確認された。
また、比較例３のように、シリコーン未変性ポリアクリル酸エステル樹脂を添加しても、Ｔｇが１００℃を超えている場合には、耐屈曲性の向上に寄与しないことも確認された。
As far as the bending resistance of Examples 1 to 12 is seen, it has a bending resistance of 6 mm or less, is excellent in bending resistance, and cracks and the like occur in the release agent layer even with repeated use of the synthetic leather process paper. It was confirmed that there is little possibility of doing so.
On the other hand, it was confirmed that when the silicone-unmodified polyacrylic acid ester resin was not added as in Comparative Examples 1 and 2, or when the amount added was small as in Comparative Example 4, the bending resistance was significantly reduced. It was.
It was also confirmed that even if the silicone-unmodified polyacrylic acid ester resin was added as in Comparative Example 3, it did not contribute to the improvement of the bending resistance when the Tg exceeded 100 ° C.
Claims (6)
前記剥離剤層は、シリコーン変性アクリル樹脂およびメラミン樹脂からなる剥離主剤が８０質量％以下２０質量％以上と、ガラス転移点が１００℃以下のシリコーン未変性ポリアクリル酸エステル樹脂が２０質量％以上８０質量％以下とからな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 contains 80% by mass or less and 20% by mass or more of a release main agent composed of a silicone-modified acrylic resin and a melamine resin, and 20% by mass or more of a silicone-unmodified polyacrylic acid ester resin having a glass transition point of 100 ° C. or less. Process paper for synthetic leather consisting of mass% or less.
前記剥離剤層は、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.
The release agent layer is a process paper for synthetic leather containing a filler composed of amorphous particles in an amount of more than 0% by mass and 12% by mass or less.
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 claim 2.
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.
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 synthetic leather process paper according to claim 2 or 3.
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 process paper for synthetic leather according to any one of claims 2 to 4.
The amorphous particles are process papers for synthetic leather which are amorphous silica particles.
前記剥離主剤に、前記シリコーン未変性ポリアクリル酸エステルを添加して混合する工程と、
混合液を前記基材に塗布する工程と、
前記基材に塗布された混合液を加熱して塗膜を得る工程と、
を実施する合成皮革用工程紙の製造方法。 The method for producing a process paper for synthetic leather according to any one of claims 1 to 5.
A step of adding and mixing the silicone unmodified polyacrylic acid ester to the release main agent,
The step of applying the mixed solution to the substrate and
A step of heating the mixed solution applied to the substrate to obtain a coating film, and
A method for manufacturing process paper for synthetic leather.
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| JP2019045463A Pending JP2020146890A (en) | 2019-03-13 | 2019-03-13 | Process paper for synthetic leather and manufacturing method of process paper for synthetic leather |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022202383A1 (en) * | 2021-03-26 | 2022-09-29 | リンテック株式会社 | Release sheet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60158249A (en) * | 1984-01-28 | 1985-08-19 | Shin Etsu Chem Co Ltd | Resin composition for matte type process release paper |
| JPH08209029A (en) * | 1995-02-02 | 1996-08-13 | Mizusawa Ind Chem Ltd | Spherical delustering agent for coating material and coating material composition |
| WO2009122984A1 (en) * | 2008-03-31 | 2009-10-08 | 日立化成ポリマー株式会社 | Releasing agent composition and releasing material |
| JP2017078161A (en) * | 2015-10-20 | 2017-04-27 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and release polyethylene terephthalate film |
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2019
- 2019-03-13 JP JP2019045463A patent/JP2020146890A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60158249A (en) * | 1984-01-28 | 1985-08-19 | Shin Etsu Chem Co Ltd | Resin composition for matte type process release paper |
| JPH08209029A (en) * | 1995-02-02 | 1996-08-13 | Mizusawa Ind Chem Ltd | Spherical delustering agent for coating material and coating material composition |
| WO2009122984A1 (en) * | 2008-03-31 | 2009-10-08 | 日立化成ポリマー株式会社 | Releasing agent composition and releasing material |
| JP2017078161A (en) * | 2015-10-20 | 2017-04-27 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and release polyethylene terephthalate film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022202383A1 (en) * | 2021-03-26 | 2022-09-29 | リンテック株式会社 | Release sheet |
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