TW201522075A - Process sheet - Google Patents

Abstract

To provide a process sheet which exhibits such excellent adhesion of particles that the particles can be inhibited from falling off and which exhibits an excellent matteness-imparting property. A process sheet comprising a substrate and a particle-containing release layer, wherein the particle -containing release layer comprises: a resin layer (A) formed from a composition which comprises both a hydroxyl-containing thermosetting resin and a crosslinking agent; and particles (B) which each contain a melamine compound at least in the surface.

Description

Engineering sheet

The present invention relates to an engineering sheet having a substrate and a particle-containing release layer provided on at least one side of the substrate.

When a resin sheet having a matting sensation (concavity and convexity) is formed on the surface of a synthetic leather, a cosmetic sheet, an interior material, an electromagnetic wave shielding film, or the like, a technical sheet having a release layer treated with a release film is generally used on the resin film. (release film).

The method for producing a resin sheet having a matte sensation is exemplified by applying a transfer resin to the surface of a release layer of a work sheet, drying or hardening to form a resin sheet, and then peeling off the resin sheet formed from the engineering sheet. The method.

In general, in the release layer of the sheet for engineering, in order to impart a matting feeling to a resin or the like, cerium oxide particles or polysiloxane particles are contained, and irregularities are formed on the surface of the release layer.

For example, Patent Document 1 aims to provide a release sheet suitable for producing a matte synthetic leather having a high matte finish, and discloses a release sheet having a coating together with a thermosetting resin and a matting agent. Special A matte layer (release layer) obtained by quantifying a composition for forming a matte layer of porous ceria fine particles having a specific particle diameter and surface area.

Further, in Patent Document 2, in order to provide a release sheet which can control the peeling property of the release layer so as to have a moderate peel strength and which does not change over time, a release sheet is disclosed which is attached to the substrate. The surface of the sheet is formed by a release layer containing polyoxyn resin fine particles having a network shape formed by a cubic element-extended azeosiloxane bond and having a specific average particle diameter.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 4330320

Patent Document 2: Japanese Patent No. 3109532

However, the release sheets disclosed in Patent Documents 1 and 2 have poor particle adhesion. In other words, the particles in the release layer of the release sheet described in Patent Documents 1 and 2 are peeled off by friction with the transfer resin or the resin sheet, and are mixed as foreign matter on the surface of the transfer resin or the resin sheet.

An object of the present invention is to provide a sheet for engineering which is excellent in particle adhesion and which has excellent matte finish impartability, which can suppress particle detachment.

The inventors found that it is disposed on at least one side of the substrate. The release layer containing particles is a resin layer formed of a thermosetting resin having a hydroxyl group and a component containing a crosslinking agent, and an engineering sheet having at least a particle containing a melamine-based compound, thereby solving the above problems. Complete the benzene invention.

That is, the present invention provides the following [1] to [8].

[1] An engineering sheet comprising a substrate and a release sheet containing particles, wherein the particle-containing release layer has a thermosetting resin having a hydroxyl group and a crosslinking agent. The resin layer (A) formed of the components and the particles (B) containing at least the surface of the melamine-based compound.

[2] The engineering sheet according to the above [1], wherein the particles (B) are composite particles containing a melamine-based compound and cerium oxide.

[3] The engineering sheet according to the above [1], wherein the content of the particles (B) of the particle-containing release layer is 6 to 45% by mass.

[4] The engineering sheet according to any one of the above [1], wherein the thermosetting resin having a hydroxyl group is selected from the group consisting of bisphenol A type epoxy resin ester and alkyd resin. More than one kind of resin.

[5] The engineering sheet according to any one of [1] to [4] wherein the crosslinking agent is a melamine-based compound.

[6] The engineering sheet according to the above [5], wherein the melamine-based compound of the crosslinking agent is hexamethoxymethylmelamine or a polymer thereof.

[7] The engineering sheet according to any one of the above [1], wherein the particle-containing release layer has an arithmetic mean surface roughness (Ra) of 0.25 to 1.50 μm.

[8] The engineering sheet according to any one of the above [1], wherein the particle-containing release layer has a maximum peak height (Rp) of 1.50 to 8.00 μm.

The sheet for engineering of the present invention has excellent particle adhesion which can suppress particle detachment and has excellent matte feeling imparting property.

1‧‧‧Engineering sheets

2‧‧‧Substrate

3‧‧‧Mold release layer containing particles

4‧‧‧Resin layer (A)

5‧‧‧ particles (B)

Film thickness of X‧‧‧ resin layer (A)

Fig. 1 is a cross-sectional view showing an engineering sheet according to an embodiment of the engineering sheet of the present invention.

[Engineering sheet]

The engineering sheet of the present invention has a substrate and a release layer containing particles, and the release layer containing particles has a resin layer (A) formed of a thermosetting resin having a hydroxyl group and a component containing a crosslinking agent. The particles (B) containing at least a melamine-based compound on the surface.

Fig. 1 is a cross-sectional view showing an engineering sheet according to an embodiment of the engineering sheet of the present invention.

The engineering sheet of the present invention is exemplified by, for example, the following engineering sheet 1 having a substrate 2 and containing on at least one side of the substrate 2. The release layer 3 of the particles and the particle-containing release layer 3 have a resin layer 4 and particles 5.

The engineering sheet 1 of Fig. 1 has a structure in which the substrate 2 and the release layer 3 containing particles are directly laminated, but may have other layers.

For example, in order to increase the adhesion between the substrate 2 and the particle-containing release layer 3, it may be an engineering sheet having an easy adhesion layer between the substrate 2 and the particle-containing release layer 3. The material forming the easy-adhesion layer is exemplified by a composition containing a thermosetting resin constituting the resin layer (A).

Further, the engineering sheet of the present invention may have an antistatic layer containing an antistatic agent.

In the engineering sheet of the present invention, the antistatic layer may be provided between the substrate 2 and the release layer 3 containing particles, or on the opposite side of the substrate 2 to the surface of the release layer 3 containing the particles. Wait.

Examples of the antistatic agent include cationic compounds such as a quaternary ammonium salt, a pyridinium salt, and a first to third amino group; and an anionic property such as a sulfonate group, a sulfate group, a phosphate group, or a phosphate group. a compound; an amphoteric compound such as an amino acid or an amine sulfate; a nonionic compound such as an amino alcohol, a glycerin or a polyethylene glycol.

<Substrate>

The substrate used in the present invention may be any one as long as it can support a release layer containing particles described later, and can be appropriately selected depending on the use of the sheet for engineering.

Examples of the substrate include a paper substrate, a substrate made of a resin film or a sheet, and a substrate obtained by laminating a paper substrate with a resin.

The paper constituting the paper substrate is exemplified by, for example, a sheet paper, a medium paper, a top paper, an impregnated paper, a coated tissue, a coated paper, a sulfuric acid paper, a glasse paper, or the like.

The resin constituting the resin film or sheet is exemplified by a polyolefin resin such as polyethylene or polypropylene; a vinyl system such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer or ethylene-vinyl alcohol copolymer. Resin; polyester resin such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate; polystyrene, acrylonitrile-butadiene-styrene copolymer, triacetic acid Cellulose, polycarbonate, etc.

A substrate obtained by laminating a paper base material with a resin is a laminate paper obtained by laminating the paper base material with a thermoplastic resin such as polyethylene.

In the base material, the base material made of a resin film or a sheet is preferably a base material made of a polyester resin film or a sheet, and has a moderate strength and is easy to obtain. More preferably, it is a substrate made of a polyethylene terephthalate (PET) film or sheet.

Further, when a substrate made of a resin film or a sheet is used as a substrate, the adhesion of the substrate to the release layer containing the particles can be improved, and the particles can be provided on the substrate. A physical or chemical surface treatment such as an oxidation method is applied to the side of the mold layer.

The oxidation method is exemplified by, for example, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like.

These surface treatments are appropriately selected depending on the type of the substrate, but it is preferably a corona discharge treatment method. In addition, a primer treatment can also be applied.

The thickness of the substrate is appropriately set according to the use of the engineering sheet However, in terms of operability and economy, it is preferably from 1 to 300 μm, more preferably from 5 to 200 μm, even more preferably from 10 to 125 μm.

When the thickness of the substrate is 1 μm or more, problems such as wrinkles are less likely to occur, and workability is improved. On the other hand, when the thickness of the substrate is 300 μm or less, the cost can be suppressed, and it is preferable from the viewpoint of economy.

<Mold release layer containing particles>

The particle-containing release layer of the engineering sheet of the present invention has a resin layer (A) formed of a thermosetting resin having a hydroxyl group and a component containing a crosslinking agent, and at least a particle containing a melamine-based compound on the surface ( B).

The resin layer (A) constituting the release layer containing particles is formed of a component containing a thermosetting resin having a hydroxyl group. In the resin layer (A), the hydroxyl group of the thermosetting resin and the melamine-based compound which is present on the surface of the particle (B) are reacted by heat hardening, so that the resin layer (A) and the particle (B) are strongly bonded. In the case of the structure, the sheet for engineering of the present invention exhibits excellent particle adhesion which can suppress the falling off of the particles (B).

In addition, since the particles (B) are present in a dot shape, irregularities are formed on the surface of the release layer containing the particles, and the unevenness can be imparted to the surface of the transfer resin or the like applied to the engineering sheet. Sense of matte.

The arithmetic mean surface roughness (Ra) of the particle-containing release layer of the engineering sheet of the present invention is preferably from 0.25 to 1.50 μm, more preferably from 0.30 to 1.30 μm, still more preferably from 0.40 to 1.00 μm.

When Ra is 0.25 μm or more, it can be used as an engineering sheet having excellent matting property. On the other hand, if Ra is 1.50 μm or less, it can be suppressed. The particles (B) fall off from the release layer containing the particles.

The maximum peak height (Rp) of the particle-containing release layer of the engineering sheet of the present invention is preferably from 1.50 to 8.00 μm, more preferably from 1.70 to 7.50 μm, still more preferably from 2.00 to 7.00 μm.

When Rp is 1.50 μm or more, it can be used as an engineering sheet having excellent matte feeling impartability. On the other hand, when Rp is 8.00 μm or less, it is possible to suppress the particles (B) from falling off from the release layer containing the particles.

Further, in the present invention, the values of Ra and Rp of the release layer containing particles are values measured in accordance with JIS B 0601-1994, specifically, the values measured by the methods described in the examples.

The ratio of the average particle diameter (diameter) of the particles (B) to the film thickness of the resin layer (A) [particle (B) / resin layer (A)] is preferably from 1.2/1.0 to 8.0/1.0, more preferably 1.6/. 1.0~7.3/1.0, and better 2.0/1.0~6.8/1.0.

When the ratio is 1.2/1.0 or more, it can be used as an engineering sheet having excellent matte feeling impartability. On the other hand, when the ratio is 8.0/1.0 or less, the area of the resin layer (A) and the particle (B) is sufficiently increased, and the excellent particle adhesion which suppresses the falling of the particles (B) is exhibited.

Further, the film thickness of the resin layer (A) is a thickness indicated by X in Fig. 1 and indicates the thickness of the resin layer 4 in the portion of the release layer 3 containing particles which is not present in the particles (B).

<Resin layer (A)>

The resin layer (A) is formed of a component containing a thermosetting resin having a hydroxyl group and a crosslinking agent.

The thermosetting resin having a hydroxyl group is exemplified by, for example, a phenol resin, a cresol resin, a resorcin resin, a xylenol resin, a naphthol resin, a bisphenol A resin, a bisphenol F resin, an epoxy resin aralkyl phenol resin, a phenolic resin such as a biphenyl aralkyl phenol resin; a hydroxyl group-containing epoxy resin such as a bisphenol A epoxy resin, a bisphenol A epoxy resin ester, or a bisphenol F epoxy resin; or a hydroxyl group-containing polyester resin; Hydroxyl-containing urethane resin; hydroxyl-containing polyoxyl resin; alkyd resin, and the like.

Among these, from the viewpoint of the strength of the resin layer (A) after hardening and the adhesion between the substrate and the resin layer (A), it is preferably selected from a bisphenol A type epoxy resin ester and a hydroxyl group. One or more resins of the polyester resin and the alkyd resin are more preferably a bisphenol A epoxy resin ester or an alkyd resin.

The crosslinking agent may be a compound which crosslinks the above-mentioned thermosetting resin having a hydroxyl group, but may react with the particles (B) to improve the excellent particle adhesion which can further suppress the falling of the particles (B). In general, a melamine-based compound is preferred.

The melamine-based compound is exemplified by, for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like (resin).

Among these, hexamethoxymethylmelamine or a polymer thereof is preferred from the viewpoint of improving the solvent resistance of the resin layer (A).

The content ratio of the thermosetting resin having a hydroxyl group to the crosslinking agent in the component constituting the resin layer (A) [thermosetting resin/crosslinking agent having a hydroxyl group] (mass ratio) forms solvent resistance and peelability. From the viewpoint of the resin layer excellent in both, it is preferably 15/85 to 98/2, more preferably 40/60~ 95/5, better for 60/40~90/10, and even better for 70/30~85/15.

Further, the total content of the thermosetting resin having a hydroxyl group and the crosslinking agent is preferably 60 to 100% by mass, more preferably 70 to 99.9% by mass, and more preferably the total amount of the components constituting the resin layer (A). It is 80 to 99.5 mass%, and more preferably 90 to 99 mass%.

The component constituting the resin layer (A) preferably further contains an acid catalyst from the viewpoint of promoting the reaction at the time of forming the resin layer (A).

As the acid catalyst, a known catalyst which is known as a crosslinking reaction catalyst having a thermosetting resin having a hydroxyl group and a crosslinking agent is suitably used, but p-toluenesulfonic acid, methanesulfonic acid, and dodecane are used. Benzobenzenesulfonic acid is preferred.

The amount of the acid catalyst used is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1 to 5, based on 100 parts by mass of the total of the thermosetting resin having a hydroxyl group and the crosslinking agent. Parts by mass.

Further, as the component constituting the resin layer (A), other components other than the thermosetting resin having a hydroxyl group, a crosslinking agent, and an acid catalyst may be used.

The other component is exemplified by a thermosetting resin such as an acrylic resin having no hydroxyl group, an antistatic agent, and the like.

The film thickness of the resin layer (A) (the thickness of the flat portion of the protrusion of the particles removed as shown in Fig. 1) is preferably from 0.3 to 5.0 μm, more preferably from 0.4 to 4.0 μm, still more preferably from 0.5 to 2.5 μm.

<Particle (B)>

The particles (B) are particles containing at least a melamine-based compound on the surface.

The melamine-based compound which is present on the surface of the particle (B) reacts with the hydroxyl group of the thermosetting resin of the resin layer (A) to form a release layer containing particles which can suppress particle detachment, and can have excellent particle adhesion. Engineering sheet.

The melamine-based compound is exemplified by, for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like (resin).

Among these, hexamethoxymethylmelamine or a polymer thereof is preferred from the viewpoint of improving the solvent resistance of the resin layer (A).

The particles (B) may be at least a single particle of a melamine-based compound, or may be a composite particle containing an inorganic material and/or an organic material together with the melamine-based compound.

The inorganic material is exemplified by, for example, calcium carbonate, kaolin, talc, clay, titanium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium hydroxide, and aluminum hydroxide.

The organic materials are exemplified by polystyrene, polypropylene, tetrafluoroethylene resin, polyoxyxylene resin, starch, and acrylic resin.

The form of the composite particles is a composite particle obtained by partially or wholly covering a surface of a core particle made of an inorganic material and/or an organic material with a melamine-based compound, or a particle formed of a melamine-based compound. The inorganic material and/or the organic material has a layered structure of composite particles or the like.

In these, it is based on even if the engineering sheet is pressed by a press machine or the like. The thermal compression also has a strength which does not cause the shape of the particles (B) to collapse, and is excellent in heat resistance. It is preferably a composite resin containing a melamine-based compound and cerium oxide, and more preferably a melamine-based compound. On the inner side of the formed particles, the cerium oxide is present in a layered structure as a composite resin.

The average particle diameter (diameter) of the particles (B) is preferably from 1.0 to 8.0 μm, more preferably from 1.3 to 7.5 μm, still more preferably from 1.7 to 7.0 μm.

Further, the value of the average particle diameter of the particles (B) means a value measured by the method described in the examples.

Further, in the present invention, two or more kinds of particles (B) having an average particle diameter within the above range may be used in combination.

The content of the particles (B) of the release layer containing particles is preferably from 6 to 45% by mass, more preferably from 7 to 40% by mass, still more preferably from 8 to 35% by mass, even more preferably from 9 to 30% by mass. %.

When the content of the particles (B) is 6% by mass or more, it can be used as an engineering sheet which is excellent in imparting a matte feeling to the surface of the resin sheet. On the other hand, when the content of the particles (B) is 45% by mass or less, the particles (B) can be prevented from falling off from the release layer containing the particles. Moreover, a uniform coated surface can be formed.

[Manufacturing method of engineering sheet]

The manufacturing method of the sheet for the present invention is not particularly limited.

For example, it is possible to prepare a release layer containing particles by blending each component such as a thermosetting resin having a hydroxyl group constituting the resin (A), a crosslinking agent, and an acid catalyst, and particles (B) with an organic solvent. After the solution, the solution is coated A coating film is formed on the substrate, and the coating mold is dried and hardened to be produced.

The organic solvent may be appropriately selected from the group consisting of the components constituting the resin layer (A) and being inert to the components, and examples thereof include toluene, xylene, methanol, ethanol, and isopropyl alcohol. Isobutanol, n-butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and the like.

These organic solvents may be used singly or in combination of two or more.

The solid content concentration of the solution for forming a release layer containing particles is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, even more preferably from 15 to 30% by mass.

The coating method is exemplified by, for example, a bar coating method, a reverse roll coating method, a knife coating method, a roll coating method, a gravure coating method, an air knife coating method, a blade coating method, and the like.

After the coating film is formed, the coating film is heated to remove the organic solvent in the coating film, and the hydroxyl group of the thermosetting resin is reacted with the melamine compound of the particle (B) to form a particle-containing mold release capable of suppressing particle shedding. Floor.

The heating temperature at this time is preferably from 80 to 180 ° C, more preferably from 100 to 160 ° C, and the heating time is preferably from 15 seconds to 5 minutes, more preferably from 20 seconds to 3 minutes.

The engineering sheet of the present invention is used for coating a transfer resin and forming a film to produce a resin sheet having a surface shape imparting a matte feeling. The resin sheet to which the matte feeling is applied is exemplified by synthetic leather, cosmetic sheet, interior material, electromagnetic wave shielding film, and the like.

The resin used as the transfer resin is exemplified by, for example, polyaminocarboxylic acid. Ester resin, polyacrylic resin, polyvinyl chloride resin, cellulose acetate, cellulose triacetate, polycarbonate, polyvinyl alcohol, and the like.

These resins are dissolved in a solvent such as an organic solvent or an aqueous solvent or dispersed in a dispersion medium, and various additives such as a plasticizer are dissolved as necessary to prepare a transfer resin having a coatable viscosity. The transfer resin is applied onto the release-treated surface of the engineering sheet, and after drying, the sheet for engineering is peeled off, whereby a resin sheet having a desired matte feeling is obtained.

In the production of the resin sheet having the matte sensation, when the sheet for engineering of the present invention is used, the particles in the release layer can be prevented from falling off, so that the portion where the matte sensation disappears does not occur, and the particles are not mixed as foreign matter to obtain a design. Excellent resin sheet.

[Examples]

The measurement methods of various physical properties in the following examples and comparative examples, and the evaluation methods of the obtained engineering sheets are as follows.

<Thickness of Resin Layer>

The thickness of the flat portion excluding the protruding portion of the resin layer of the engineering sheet was measured as the film thickness of the resin layer using a scanning electron microscope (product name "VE-9800S" manufactured by KEYENCE Co., Ltd.).

<Average particle size of particle components>

Using methyl ethyl ketone as a dispersion medium, a dispersion of a particle component having a solid concentration of 5 mass% was prepared. Next, using laser diffraction scattering The particle size distribution measuring apparatus (product name "LA-920" manufactured by Horiba, Ltd.) was used to measure the average particle diameter of the particle component.

<Ra, Rp of engineering sheets>

The surface of the release layer containing particles of the engineering sheet produced in the examples and the comparative examples was measured by a contact surface roughness meter (manufactured by Mitu Toyo Co., Ltd., product name "SV3000S4") in accordance with JIS B 0601-1994. Average surface roughness (Ra) and maximum peak height (Rp).

<particle adhesion>

Weighed and rubbed the friction fastness tester "RT-200" (product name, manufactured by Daiei Chemical Seiki Seisakusho Co., Ltd.) by crimping and sliding, using a non-stretch polypropylene film having a thickness of 80 μm, and making it in the examples and comparative examples. The surface of the release layer containing the particles of the engineering sheet was ground 50 times with a load of 1 kg.

Next, the surface of the particle-containing release layer of the polished engineering sheet was observed by a visual observation and a scanning electron microscope, and the particle component was peeled off (falling powder), and the particle adhesion of the engineering sheet was evaluated based on the following criteria.

A: The presence or absence of a particle component on the surface of the particle-containing release layer of the engineering sheet was observed, and the ratio of the number of particles falling off (falling powder) was less than 3%.

B: The presence or absence of a particle component on the surface of the particle-containing release layer of the sheet for engineering was observed, and the ratio of the number of particles of the falling (falling powder) was 3% or more and less than 10%.

C: Observe the presence or absence of particles on the surface of the particle-containing release layer of the engineering sheet. The ratio of the number of particles of the fraction and the falling (falling powder) is 10% or more.

<The turbidity value of the resin sheet>

The transfer resin was applied to the engineering sheets produced in the examples and the comparative examples, and then peeled off to obtain a resin sheet, and the haze value of the resin sheet was measured to evaluate the matte feeling impartability of the sheet for engineering.

As the transfer resin, an acrylic copolymer (MMA/2HEMA = 95/5 (% by mass)) composed of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (2HEMA) was used.

Specifically, the solution of the above-mentioned transfer resin (solid content: 30% by mass) was applied onto the surface of the particle-containing release layer of the engineering sheets of the examples and the comparative examples, and dried to form a resin sheet having a thickness of 60 μm. Then, the resin sheet was peeled off from the sheet for engineering, and the haze value of the resin sheet was measured in accordance with JIS K 7136-2000 using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH2000").

The haze value of the resin sheet is an index indicating the degree of unevenness of the surface of the resin sheet. When the haze value of the resin sheet is large, the degree of unevenness on the surface of the resin sheet is large, and the haze value of the resin sheet is small, and the degree of unevenness on the surface of the resin sheet is small. That is, the matte feeling imparting property of the sheet for engineering can be evaluated based on the turbidity value of the resin sheet.

Further, the resin sheet when the resin sheet was formed on the release-treated glass had a haze value of 0.1%.

The above "released glass" is applied to soda lime glass (100 mm × 100 mm × 5 mm) with a solid concentration of Meyer bar #4. A toluene solution of a 2% by mass of a release agent was formed into a coating film, and the coating film was heat-cured at 150 ° C for 1 minute. The type and amount of the release agent used are shown below.

‧"KS-847H" (trade name, Shin-Etsu Chemical Co., Ltd., solid content concentration: 30% by mass): 100 parts by mass (solid content)

‧ "PL-50T" (trade name, Shin-Etsu Chemical Co., Ltd., solid content concentration: 2% by mass): 1 part by mass (solid content)

Examples 1 to 11 and Comparative Examples 1 to 2

80 parts by mass of a bisphenol A type epoxy resin ester having a hydroxyl group thermosetting resin and 20 parts by mass of a melamine resin of a crosslinking agent (manufactured by Hitachi Chemical Co., Ltd., trade name "TA31-059D" , solid content: 50%, solvent: xylene/toluene/isobutanol=36/32/32 (mass ratio) mixed solvent) 100 parts by mass of solid component added 2.5 parts by mass (solid content) of p-toluene An acid methanol solution (solid content concentration: 50% by mass) was used as an acid catalyst to prepare a solution of the resin composition.

Then, the particle component of the type and the amount of the formulation shown in Table 1 was added to the solution of the resin composition, and diluted with a mixed solvent of toluene/methyl ethyl ketone = 30/70 (mass ratio) to prepare a release layer. Use a solution. Further, the solid content concentration of the solution for forming a release layer was adjusted to 18% by mass in Examples 1 to 3, 10, and 11 and Comparative Examples 1 and 2, and was adjusted to 24% by mass in Examples 4 to 9. . Further, in Examples 10 to 11, the solution for forming a release layer was adjusted by using two kinds of particles (B) containing a melamine-based compound.

Next, polyethylene terephthalate having a thickness of 50 μm on the substrate On one surface of a (PET) film (manufactured by TORAY Co., Ltd., trade name "S10"), the solution for forming a release layer containing the particles described above was applied to various types of wheat rods to form a coating film. Next, the coating film was heat-cured at 150 ° C for 1 minute to form a resin layer having a film thickness as described in Table 1, and a sheet for engineering having a release layer containing particles on the PET film was produced.

Example 12

Alkyd resin having a thermosetting resin having a hydroxyl group (manufactured by Hitachi Chemical Co., Ltd., trade name "TESLAC 2052-60T", solid content concentration: 60% by mass, solvent: toluene/xylene = 85/15 (mass ratio) 20 parts by mass of the solid content of the mixed solvent), 20 parts by mass (solid content) of melamine resin (manufactured by Cytec Industries Co., Ltd., trade name "CYMEL 303", solid content concentration: 100%) as a crosslinking agent, and further A solution of a resin composition was prepared by adding 2.5 parts by mass of a solid solution of p-toluenesulfonic acid in methanol (solid content concentration: 50% by mass) as an acid catalyst.

Next, the particle component of the type and the amount of the formulation shown in Table 1 was added to the solution of the resin composition, and diluted with a mixed solvent of toluene/methyl ethyl ketone = 30/70 (mass ratio) to prepare a solid concentration of 18 % by mass of the solution for forming a release layer.

Then, using the prepared solution for forming a release layer, a sheet for engineering having a release layer containing particles on a PET film was produced in the same manner as in Example 1.

The particle components used in the examples and comparative examples are as follows.

‧ "OPTBEADS ^® 2000M": The product name, Nissan Chemical Industry Co., Ltd., a composite particle having a structure in which cerium oxide exists in a layered shape from the innermost surface of the melamine tri-resin particle at about 100 nm. 1.65, average particle diameter: 2.0 μm.

‧ "OPTBEADS ^® 3500M": The product name, Nissan Chemical Industry Co., Ltd., a composite particle having a structure in which cerium oxide exists in a layered shape from the innermost surface of the melamine tri-resin particle at about 100 nm. 1.65, average particle diameter: 3.5 μm.

‧ "OPTBEADS ^® 6500M": The product name, Nissan Chemical Industry Co., Ltd., a composite particle having a structure in which cerium oxide exists in a layered shape from the innermost surface of the melamine tri-resin particle at about 100 nm. 1.65, average particle diameter: 6.5 μm.

‧ "NIPSIL SS-50B": trade name, manufactured by TOSOH‧SILICA (shares), porous amorphous cerium oxide particles.

‧ "TOSPEARL 120": trade name, Momentive Performance Materials Japan (shares), polyfluorene oxide particles, average particle size: 2.0 μm, true specific gravity: 1.32.

The engineering sheets of Examples 1 to 12 have excellent particle adhesion, and the haze value of the resin sheet is high, and the matte feeling impartability of the sheet for engineering is also good.

On the other hand, in the engineering sheets of Comparative Examples 1 and 2, since the particles were rubbed against the non-stretched polypropylene film, the particles were detached from the release layer containing the particles, and the particles were inferior in particle adhesion. In particular, the engineering sheet of Comparative Example 1 was found to be damaged by the friction of the porous amorphous ceria of the particle component.

[Industrial availability]

The sheet for engineering of the present invention can be used for the production of a resin sheet having a matte feeling (concavity and convexity) on the surface of a synthetic leather, a cosmetic sheet, an interior material, and an electromagnetic wave shielding film.

Claims (8)

An engineering sheet comprising a substrate and a release sheet containing particles, wherein the particle-containing release layer is formed of a component containing a thermosetting resin having a hydroxyl group and a crosslinking agent. The resin layer (A) and the particles (B) containing at least a melamine-based compound on the surface. The engineering sheet according to claim 1, wherein the particles (B) are composite particles containing a melamine-based compound and cerium oxide. The engineering sheet according to claim 1 or 2, wherein the content of the particles (B) of the particle-containing release layer is 6 to 45% by mass. The engineering sheet according to any one of claims 1 to 3, wherein the thermosetting resin having a hydroxyl group is one or more resins selected from the group consisting of bisphenol A epoxy resin esters and alkyd resins. The engineering sheet according to any one of claims 1 to 4, wherein the crosslinking agent is a melamine-based compound. The engineering sheet according to claim 5, wherein the melamine-based compound of the crosslinking agent is hexamethoxymethylmelamine or a polymer thereof. The engineering sheet according to any one of claims 1 to 6, wherein the particle-containing release layer has an arithmetic mean surface roughness (Ra) of 0.25 to 1.50 μm. The engineering sheet according to any one of claims 1 to 7, wherein the particle-containing release layer has a maximum peak height (Rp) of 1.50 to 8.00 μm.