CN104640704B

CN104640704B - Sheet material, decoration sheet and adhesiveness decoration sheet are used in printing

Info

Publication number: CN104640704B
Application number: CN201380044716.5A
Authority: CN
Inventors: 福田升平; 濑口诚司; 清水滋吕; 宫崎樱; 藤木保武
Original assignee: Oji Paper Co Ltd
Current assignee: New Oji Paper Co Ltd
Priority date: 2012-08-31
Filing date: 2013-08-30
Publication date: 2017-11-14
Anticipated expiration: 2033-08-30
Also published as: JPWO2014034850A1; KR20150038591A; WO2014034850A1; JP5850165B2; TWI555639B; TW201418015A; KR101610041B1; CN104640704A

Abstract

The present invention relates to a kind of printing sheet material, it is the printing sheet material for including plastic basis material and lamination in the planographic printing plate of the hardening resin layer of at least one side of the plastic basis material, and the hardening resin layer includes hardening resin and pigment, the pigment is the inorganic fine particles of the average grain diameter with 5~90nm and surface through silicic acid anhydride, and the thickness of the hardening resin layer is 0.1~15 μm.According to the present invention it is possible to a kind of resistance to adhesive when being printed using lithographic plate, printing adaptability and the excellent printing sheet material of the transparency are provided, implement decoration sheet and adhesiveness decoration sheet that printing forms to the printing sheet material.

Description

Sheet material, decoration sheet and adhesiveness decoration sheet are used in printing

Technical field

The present invention relates to a kind of printing sheet material, implement decoration sheet and the adhesion that printing forms to the printing sheet material Property decoration sheet.

The present invention be based on August in 2012 31 days in the Japan Patent Patent 2012-192200 that Japan files an application and CLAIM OF PRIORITY, and by its content quotation to herein.

Background technology

Have and the sheet material (decoration sheet) using the implementations such as printing decoration is fitted in formed products surface and formed products are assigned Design, or the situation on protection formed products surface.

Sheet material (printing sheet material) surface before printing is formed to improve the adhesion with printing layer in most cases Tackifier coating (anchor coat).

However, in the case where being printed using lithographic plate to printing with sheet material, if forming tackifier coating, that Printing sheet material and lithographic plate is touched (adhesion, blocking), as a result become easily to produce the printing such as deinking Failure.

Moreover, printing is typically and to be used as roll by continuous coiling in the state of continuous strip of sheet material with sheet material Transported, keeping.

However, in the case where the printing for foring tackifier coating is coiled into web-like with sheet material, also have tackifier coating and The easy adhesion of sheet substrate abutted with tackifier coating, the problem of being as a result not easy with sheet material to extract the printing of web-like out.

Then, as when printing is coiled into web-like with sheet material, tackifier coating and the sheet material base with tackifier coating adjoining Material is not easy the film touched, such as in patent document 1, discloses a kind of lamination film roll cylinder, and it is that surface is had into following thickening The hyaline membrane of coating coils into web-like and formed, and the tackifier coating includes the inorganic particulate with 0.1~5.0 μm of average grain diameter. In patent document 1, disclose by adding inorganic particulate in tackifier coating, the surface roughness (Ra) of tackifier coating turns into 0.015~0.060 μm, resistance to adhesive during so as to show to batch.

Background technology document

Patent document

Patent document 1：Japanese Patent Laid-Open 2010-253784 publications

The content of the invention

[problems to be solved by the invention]

But also there is the situation that decoration sheet is fitted in the optical component such as display or touch panel.Therefore, for Decoration sheet also requires the excellent transparency.

However, the lamination film roll cylinder described in patent document 1 does not obtain the sufficiently transparency.

It is an object of the invention to provide it is a kind of printed using lithographic plate when resistance to adhesive, printing adapt to Property and the excellent printing sheet material of the transparency, implement decoration sheet that printing forms to the printing sheet material and adhesiveness fills Spike material.

[technological means for solving problem]

The present invention has following form.

[1] a kind of printing sheet material, it is the printing sheet material for being printed using lithographic plate, and is had Plastic basis material and the hardening resin layer comprising hardening resin and pigment formed on the plastic basis material, the pigment The inorganic fine particles for being 5~90nm for average grain diameter of the surface through silicic acid anhydride, and the thickness of the hardening resin layer is 0.1~15 μm.

[2] the printing sheet material according to described in [1], wherein according to ASME (American Society of Mechanical Engineers, American Society of Mechanical Engineers (AMSE)) the hardening resin layer measured by B46.12 surface Arithmetic average roughness (Ra) be 0.5~15nm.

[3] a kind of decoration sheet, it is on the hardening resin layer of the printing sheet material described according to [1] or [2] Form printing layer.

[4] a kind of adhesiveness decoration sheet, it is on the surface of the plastic basis material side of the decoration sheet described according to [3] Form adhesion layer.

That is, the present invention has following form.

<1>A kind of printing sheet material, it is the hard of at least one side that includes plastic basis material and lamination in the plastic basis material The printing sheet material of the planographic printing plate of change type resin bed, and

The hardening resin layer includes hardening resin and pigment, and the pigment is the average grain diameter with 5~90nm And inorganic fine particles of the surface through silicic acid anhydride, and

The thickness of the hardening resin layer is 0.1~15 μm；

<2>According to<1>Described printing sheet material, wherein the hardening resin measured by according to ASME B46.12 The arithmetic average roughness (Ra) on the surface of layer is 0.5~15nm；

<3>A kind of decoration sheet, it is in basis<1>Or<2>Lamination on the hardening resin layer of described printing sheet material Printing layer；

<4>A kind of adhesiveness decoration sheet, it is in basis<3>The adhesion of at least one side lamination of described decoration sheet Layer.

[invention effect]

According to the present invention it is possible to provide a kind of resistance to adhesive when being printed using lithographic plate, printing adaptability, And the excellent printing sheet material of the transparency, implement decoration sheet and the adhesiveness cosmetic sheet that printing forms to the printing sheet material Material.

Brief description of the drawings

Fig. 1 is the sectional view of one for representing printing sheet material.

Fig. 2 is the sectional view of other for representing printing sheet material.

Fig. 3 is the sectional view of other for representing printing sheet material.

Fig. 4 is the sectional view of one for representing decoration sheet.

Fig. 5 is the sectional view of one for representing adhesiveness decoration sheet.

Fig. 6 is the sectional view of another for representing adhesiveness decoration sheet.

Fig. 7 is the sectional view of other for representing adhesiveness decoration sheet.

Fig. 8 is the sectional view of other for representing adhesiveness decoration sheet.

Embodiment

Hereinafter, the present invention is described in detail.

[printing sheet material]

Fig. 1 is the sectional view of the composition for the printing sheet material for being denoted as one embodiment of the present invention example.

The printing of this sheet material 10 has plastic basis material 11 and forms the hardening resin on the plastic basis material 11 Layer 12.

In addition, in the form of the present invention, preferably 20~200 μm of the thickness of printing sheet material, more preferably 30~120 μ m.In addition, the thickness can use contact pin type film thickness gauge (for example, the manufacture of Mitutoyo companies has peak holding (peak Hold) ABS (absolute, absolute origin) digital display dial gauge (digimatic indicator) ID-C112A of function) carry out Measure.

As plastic basis material 11, as long as there is the transparency, then be not particularly limited, on the transparent of plastic basis material 11 Property, it is more than 85% preferably according to the total light transmittance measured by JIS K 7361.That is, in the form of the present invention, close In the transparency of plastic basis material 11, preferably total light transmittance is more than 85%, and the total light transmittance is defined as using 100mm × 100mm test piece, with CIE (Commission Internationale de L ' Eclairage, international lighting committee Member's meeting) the light D65 of standard be used as light source, the total light beam that passes through integrated using integrating sphere of test piece is relative to parallel input light The ratio of beam.In addition, the total light transmittance more preferably 85~95%, further preferred 88~92%.

As the material of plastic basis material 11, such as can enumerate：PET (PET, Polyethylene Terephthalate), PEN, polytrimethylene terephthalate, polybutylene terephthalate, poly- naphthalene two Formic acid propylene diester, polyethylene, polypropylene, diacetyl cellulose, triacetyl cellulose, acetylcellulose butyrate, polyvinyl chloride, It is polyvinylidene chloride, polyvinyl alcohol, vinyl-vinyl acetate copolymer, polystyrene, makrolon, polymethylpentene, poly- Sulfone, polyether-ketone, polyether sulfone, PEI, polyimides, fluororesin, polyamide, acrylic resin etc..

Wherein, for the viewpoints such as the transparency, weatherability, solvent resistance, rigidity, cost, preferably PET.

In plastic basis material 11, various additives can also be included.As additive, such as can enumerate：Antioxidant, Heat-resisting stabilizing agent, ultra-violet absorber, organic filler, inorganic particulate, pigment, dyestuff, antistatic additive, nucleator, coupling agent etc..

Surface treatment can also be implemented to plastic basis material 11 to be used for improving the close of plastic basis material 11 and hardening resin layer 12 Connecing property.As surface treatment, such as can enumerate：Utilize the further provided for contouring processing of the progress such as blasting treatment or solvent processing, corona Discharge process, chromic acid processing, flame treatment, hot blast are handled, at the surface oxidation using the progress such as ozone, ultraviolet treatment with irradiation Reason etc..

Preferably 10~500 μm, more preferably 20~300 μm of the thickness of plastic basis material 11.If the thickness of plastic basis material 11 is More than 10 μm, then plastic basis material 11 is not easy to break, if less than 500 μm, then the transparency can be maintained well, and Operability is also excellent.Here, so-called " thickness of plastic basis material 11 ", refer to use contact pin type film thickness gauge (Mitutoyo company systems The ABS digital display dial gauge ID-C112A with peak-value-holding function made) plastics before measure lamination hardening resin layer 12 The value of the gained of base material 11.

Hardening resin layer 12 is to include hardening resin and pigment, and be arranged on the most top layer of printing sheet material 10 Layer.Here, so-called " hardening resin layer ", it is intended that make the layer of the hardening resin hardening gained.In addition, so-called " most table Layer ", it is intended that sheet material 10 and air contact side the layer of printing.

Detailed content can be addressed below, and hardening resin layer 12 for example can be by that will include hardening resin and face The hardening resin layer formation of material is coated on plastic basis material 11 with composition, and makes dried coating film and hardening and obtain.Hereinafter, it is right Illustrated in each composition for forming hardening resin layer 12.

(pigment)

Pigment for hardening resin layer 12 is inorganic fine particles of the surface through silicic acid anhydride (hereinafter also referred to as " thin Aquation inorganic fine particles ").

If the hardening resin layer formation comprising hydrophobization inorganic fine particles is coated on plastic basis material 11 with composition On, then hydrophobization inorganic fine particles are partly exposed in film coated surface, and the surface of hardening resin layer 12, which turns into, has appropriateness Concavo-convex face (male and fomale(M＆F) 12a).Therefore, in the case where being printed using lithographic plate, hardening resin layer 12 It is not easy to touch with lithographic plate, resistance to adhesive can be shown.Therefore, printing sheet material implementation goal can be printed.This In, so-called " hydrophobization inorganic fine particles are partly exposed in film coated surface ", it is intended that in 1 inorganic fine particles, one part Expose in film coated surface.That is, by making the hydrophobization for including the average grain diameter with 5~90nm in hardening resin layer 12 inorganic Particulate, the hydrophobization inorganic fine particles will not be imbedded in hardening resin layer 12, and one part turns into film coated surface The state exposed, as a result, printing sheet material of the invention can show resistance to adhesive, thus preferably.Here, it is so-called " hydrophobic Change inorganic fine particles to be imbedded in hardening resin layer 12 ", it is intended that the hydrophobization inorganic fine particles are integrally configured constrictive type The state that the hardening resin of resin bed 12 is coated to.

In addition, " adhesion " in the so-called present invention, lithographic plate and print when referring to be printed using lithographic plate The hardening resin layer contiguity of brush sheet material, so-called " resistance to adhesive ", refers to the property for relaxing the adhesion.

Hydrophobization inorganic fine particles are to carry out silicic acid anhydride to the surface of inorganic fine particles to form.As silicic acid anhydride Method, as long as there is the effect of the present invention, then be not particularly limited, known method can be used, such as can lead to The inorganic agents such as the hydrophilic group for making inorganic fine particles surface and organo-silicon compound are crossed to be reacted, be replaced into the hydrophobic groups such as alkyl and Obtain.That is, in the form of the present invention, so-called " making the surface-hydrophobicized of inorganic fine particles ", it is intended that make inorganic particles sublist The hydrophilic group in face is replaced into the hydrophobic groups such as alkyl.

As inorganic fine particles, such as can enumerate：Silica, aluminum oxide, titanium oxide, zirconium oxide, zinc oxide, oxidation Metal fluoride particulates such as the metal oxide microparticles such as germanium, yttrium oxide, tin oxide, magnesium fluoride, sodium fluoride etc..In addition, Metal microparticle, metal sulfide particulate, metal nitride particulate etc. can be used.In addition, the inorganic fine particles It is preferred that average grain diameter is identical with the preferred average grain diameter of hydrophobization inorganic fine particles.

As silicic acid anhydride agent, organo-silicon compound etc. can be enumerated.

As organo-silicon compound, such as can enumerate：MTMS, dimethyldimethoxysil,ne, four Methoxy silane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, MTES, dimethyl diethoxy Base silane, tetraethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, methyl trichlorosilane, dimethyl two Chlorosilane, trimethyl monochlorosilane etc..

In addition, as inorganic agent, aliphatic acid, alcohol etc. can also be used.Specifically, can enumerate：Carbon number is more than 2 Aliphatic acid, alcohol that carbon number is more than 5 etc..

The average grain diameter of hydrophobization inorganic fine particles is 5~90nm, preferably 20~60nm.

If the average grain diameter of hydrophobization inorganic fine particles is more than 5nm, then because hydrophobization inorganic fine particles do not have It is imbedded in hardening resin layer 12 and on the surface of hardening resin layer 12, the i.e. interface of hardening resin layer 12 and air Expose, thus sufficient resistance to adhesive and printing adaptability can be obtained.Here, so-called " printing adaptability ", it is intended that ink is close Connect.On the other hand, if the average grain diameter of hydrophobization inorganic fine particles is below 90nm, then the scattering of light is reduced.Moreover, by Become too much in the bumps that can suppress the surface of hardening resin layer 12, so being not likely to produce pressure when batching printing with sheet material 10 The defects of trace.Therefore, resistance to adhesive can be assigned with the transparency of lossless hardening resin layer 12.

In addition, particle of the average grain diameter less than 5nm is difficult to manufacture and the technology of required height.It is additionally, since easy cohesion And offspring is formed, so operability is poor.

In addition, the average grain diameter of so-called hydrophobization inorganic fine particles, refers to the primary particle of hydrophobization inorganic fine particles Average grain diameter.Here, so-called " primary particle ", refer to the basic crystal grain for forming inorganic fine particles, the primary particle is condensed and Into block be referred to as 2 particles.In the form of the present invention, the inorganic fine particles contained by hardening resin layer 12 are preferably once Particle rather than blocky particle.If the inorganic fine particles are primary particle, then can obtain resistance to adhesive and the transparency Effect, thus preferably.

In addition, the average grain diameter in the so-called present invention, refers to micro- using penetrating type electron microscope or scanning electron Value measured by the observation image of mirror.Specifically, the average grain diameter of hydrophobization inorganic fine particles is determined as follows.

Using penetrating type electron microscope or scanning electron microscope, to the particle pictures of hydrophobization inorganic fine particles Maximum length (Dmax：The maximum length between 2 points on the profile of particle picture) and maximum length vertical length (DV-max：Profit When clamping particle picture with 2 straight lines parallel with maximum length, the shortest length between 2 straight lines) it is measured, its is several What average value (Dmax × DV-max)^1/2It is set to particle diameter.Particle diameter is determined to arbitrary 100 inorganic fine particles using this method, and Its arithmetic mean of instantaneous value is set to average grain diameter.

In the present invention, the preferred primary particle of inorganic fine particles.It is according to penetrating type as the method for discrimination of primary particle The observation image of electron microscope or scanning electron microscope, inorganic fine particles are separately existed in hardening resin layer Particle is referred to as primary particle, and particle existing for multiple particle buildups is referred to as into 2 particles.

The content of hydrophobization inorganic fine particles in hardening resin layer 12 is in the mass parts of hardening resin 100, and preferably 3 ~15 mass parts, more preferably 5~12 mass parts.If the content of hydrophobization inorganic fine particles is more than 3 mass parts, then can be with Obtain resistance to adhesive more excellent printing sheet material 10.

On the other hand, if the content of hydrophobization inorganic fine particles is below 15 mass parts, then it is suitable that maintenance can be formed The transparency of degree, and the hardening resin layer 12 that resistance to adhesive is more excellent.

In the form of the present invention, the pigment is preferably free of the surface not inorganic fine particles Jing Guo silicic acid anhydride (hydrophilic inorganic particulate) etc., and be only made up of hydrophobization inorganic fine particles.If pigment is only by hydrophobization inorganic fine particles Form, then resistance to adhesive or transparent more excellent printing sheet material can be obtained.

(hardening resin)

The hardening resin included as hardening resin layer 12, it can enumerate：Thermmohardening type resin, active energy ray Hardening resin etc..

As thermmohardening type resin, such as can enumerate：Phenol resin, carbamide resin, diallyl phthalate resin, three Cymel, unsaturated polyester resin, polyurethane resin, epoxy resin, amino-alkyd resin, silicones, poly- silicon Oxygen alkane resin etc..

As curable with actinic energy ray resin, preferably propenoic methyl carbamate oligomer.

Propenoic methyl carbamate oligomer via the polyoxy of carbamate key connection carbon number 2~10 stretch alkyl moiety or The saturated polyester fragment or described two fragments of carbon number 2~10, and there is acryloyl group in two ends.In addition, the acrylic acid Oligourethane preferably has 10,000~300,000 weight-average molecular weight (Mw), more preferably with 30,000 ~200,000 Mw.Here, so-called Mw, refer to use gel permeation chromatography (GPC, Gel Permeation Chromatography the value measured by).

In addition, in order to assign the function of hard conating to hardening resin layer 12, preferably using making multifunctional (methyl) propylene Acid system monomer polymerize obtained polymer as curable with actinic energy ray resin.The polymer is due to being with cross-linked structure Hard acrylic acid series polymeric compounds, so case hardness, the transparency, marresistance etc. are excellent.

" multifunctional " means there is more than 2 polymerism unsaturated groups in intramolecular, and " (methyl) acrylic monomer " is At least there is compound of (methyl) acryloyl group as polymerism unsaturated group." (methyl) acryloyl group " represents acryloyl group Or methylacryloyl.

As multifunctional (methyl) acrylic monomer, such as following monomers can be enumerated.

DPG two (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, tripropylene glycol two (methyl) Acrylate, polyethylene glycol (weight-average molecular weight 600) two (methyl) acrylate, epoxy pronane modification neopentyl glycol two (methyl) acrylate, modified bisphenol A two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, poly- second Glycol (weight-average molecular weight 400) two (methyl) acrylate etc. two functions (methyl) acrylate；

Pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane second The trifunctionals such as epoxide three (methyl) acrylate, polyethers three (methyl) acrylate, glycerine propoxyl group three (methyl) acrylate (methyl) acrylate；

Pentaerythrite four (methyl) acrylate, pentaerythrite ethyoxyl four (methyl) acrylate, two-trihydroxy methyl third Alkane four (methyl) acrylate etc. tetrafunctional (methyl) acrylate；

Dipentaerythritol five (methyl) acrylate, propionic acid are modified dipentaerythritol five (methyl) acrylate, two seasons penta (methyl) propylene more than five functions such as tetrol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate Acid esters etc..

Such multifunctional (methyl) acrylic monomer can be used alone, can also and with two or more.

Multifunctional (methyl) acrylic monomer preferably with (methyl) acrylic monomer more than tetrafunctional (preferably (methyl) acrylic monomers more than five functions) be used as principal component, using two~trifunctional (methyl) acrylic monomer as Accessory ingredient.Here, so-called " principal component ", it is intended that contain 51 in the multifunctional mass parts of (methyl) acrylic monomer 100 The composition of~100 mass parts.In addition, so-called " accessory ingredient ", it is intended that in the multifunctional mass of (methyl) acrylic monomer 100 Composition containing 0~49 mass parts in part.That is, the ratio of (methyl) acrylic monomer more than tetrafunctional is in multifunctional (first Base) acrylic monomer 100 is in mass parts, and preferably 50 mass parts are less than 95 mass parts, more preferably more than 60 mass parts And it is less than 90 mass parts.In addition, the ratio of two~trifunctional (methyl) acrylic monomer is in multifunctional (methyl) acrylic acid series In the mass parts of monomer 100, preferably 5 mass parts are less than 50 mass parts, and more preferably 10 mass parts are less than 40 mass Part.

Among such, (methyl) acrylic monomer more than tetrafunctional is favorably improved hardness, two~trifunctional (first Base) acrylic monomer be favorably improved hardening resin flexibility.Therefore, as hardening resin, in multifunctional (first Base) acrylic monomer 100 in mass parts containing the mass parts of (methyl) acrylic monomer 50 more than tetrafunctional more than And it is less than 95 mass parts, the two~trifunctional (methyl) is contained in the multifunctional mass parts of (methyl) acrylic monomer 100 In the case that the mass parts of acrylic monomer 5 are less than 50 mass parts, the hardening resin layer 12 obtained is with higher Hardness and appropriateness flexibility and excellent scratch resistance, detailed content be addressed below, hardening resin layer 12 can be made For hard conating.

Solid content of the content of hardening resin in hardening resin layer 12 in hardening resin layer formation composition In the mass parts of composition 100, preferably 82~97 mass parts, more preferably 87~92 mass parts.If the content of hardening resin is 82 More than mass parts, then can fully ensure the adhesion to plastic basis material 11.In addition, make multifunctional (methyl) third in use In the case that olefin(e) acid system monomer polymerize obtained polymer as hardening resin, sufficient hard painting propert energy is easily obtained.Separately On the one hand, if the content of hardening resin is below 97 mass %, then photopolymerization initiator or leveling agent etc. can be added For auxiliary agent as any condition, it is bad to be not likely to produce hardening, and easily maintains the hardening resin layer formation composition to modeling Expect the coating adaptability of base material 11, thus preferably.Here, so-called " sufficient hard painting propert energy ", it is intended that compared with plastic basis material resistance to It is scratch resistance more excellent.

(other compositions)

Hardening resin layer formation composition preferably contains multifunctional (methyl) acrylic monomer and light in the lump Polymerization initiators are used for promoting to harden.

As photopolymerization initiator, known photopolymerization initiator can be used, such as can enumerate：Styrax, rest in peace Fragrant methyl ether, benzoin ethyl ether, benzoin isopropyl ether, styrax n-butyl ether, benzoin isobutyl ether, acetophenone, Dimethylaminobenzene second Ketone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 2- hydroxy-2-methyl -1- phenyl third Alkane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyls-propane -1- ketone, 4- (2- Hydroxyl-oxethyl) phenyl -2 (hydroxyl -2- propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-lignocaine hexichol first Ketone, propiophenone, dichloro benzophenone, 2-methylanthraquinone, 2- EAQs, 2- tert-butyl groups anthraquinone, 2- amino anthraquinones, 2- methyl thiazoliums Ton ketone, 2- ethyls thioxanthones, CTX, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, benzil dimethyl contracting Ketone, acetophenone dimethyl ketal, to dimethylamine benzoic ether etc..Such photopolymerization initiator can be used alone, and also may be used To be used in combination of two or more.

Solid content composition 100 mass parts of the allotment amount of photopolymerization initiator in hardening resin layer formation composition In, preferably 0.5~10 mass parts, more preferably 2~8 mass parts.More than 0.5 mass parts, then be not likely to produce constrictive type The hardening of resin bed 12 is bad, thus preferably.Even if in addition, relative to hardening resin layer formation composition solid content into Point gross mass allocate the photopolymerization initiator more than 10 mass %, can not also obtain and hardening that allotment amount matches promotes Effect, and cost also uprises.In addition, there is photopolymerization initiator to remain in hardening resin layer 12 and turn into xanthochromia or ooze out The reason for worry.

In addition, in addition to photopolymerization initiator, sensitising agent and then can also be contained.As sensitising agent, such as can enumerate： N-butylamine, triethylamine, tri-n-butyl phosphine etc..

Hardening resin layer formation composition can also contain if necessary in the range of lossless effect of the invention Other compositions beyond stating.It is used for assigning hardening resin layer other functions in addition to resistance to adhesive for example, can contain The known additive of (antibiotic property, soil resistance, antistatic behaviour, UV-preventing etc.).As such additive, such as can To enumerate：For the antiseptic of endowing antibacterial, for assigning the fluorine system anti-fouling agent of soil resistance, for assigning finger sliding Fluorine system lubricant, it is sub, anti-for assigning the metal oxide microparticle of antistatic property for improving the leveling agent of coating adaptability Electrostatic resin, electroconductive polymer, for assigning the metal oxide microparticle of UV-preventing, ultra-violet absorber, light Stabilizer etc..

Hardening resin layer formation composition can also contain solvent.

As solvent, such as can use：Methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, n-hexane, just Butanol, methyl iso-butyl ketone (MIBK), methyl butyl ketone, ethyl butyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether Acetic acid esters, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, METHYLPYRROLIDONE etc..It is such can be used alone with On, two or more uses can also be mixed.

For especially can mitigates crawling, preferably and with the different two or more solvents of evaporation rate.Example Such as, preferably by least two in methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate, propylene glycol monomethyl ether Kind is used in mixed way.

(function of hardening resin layer)

Hardening resin layer 12 is played and formed using lithographic plate on hardening resin layer 12 of the printing with sheet material 10 During printing layer, the effect of printing layer and the adhesion of hardening resin layer 12 is improved.In addition, depending on hardening resin species or contain Amount is different, and the hardening resin layer 12 for the function of also having hard conating concurrently can be made.

In the case where hardening resin layer 12 also has the function of hard conating concurrently, printing sheet material 10 may be used as hard smear Material.

(thickness of hardening resin layer)

The thickness of hardening resin layer 12 can be adjusted in the range of 0.1~15 μm.

In the form of the present invention, the thickness of so-called hardening resin layer 12, it is intended that from hardening resin layer 12 and modeling Material base material 11 interface play the interface of hardening resin layer 12 and air untill thickness average value.The thickness can lead to Cross using contactless film thickness gauge (F20 that Filmetrics companies manufacture), surveyed in 380~1050nm wave-length coverage Determine and obtain.In addition, preferably 0.6~12 μm, more preferably 1~10 μm of the thickness of hardening resin layer 12.If hardening resin The thickness of layer 12 is less than 0.1 μm, then resistance to adhesive can reduce.In addition, the function of hardening resin layer 12 can not be played, right When printing implements printing with sheet material 10, i.e., in lamination printing layer on hardening resin layer 12, hardening resin layer 12 and printing The adhesion of layer reduces.On the other hand, if the thickness of hardening resin layer 12 is more than 15 μm, then hardening resin layer is in itself The transparency can reduce.In addition, when implementing to print with sheet material 10 to printing, i.e., the lamination printing layer on hardening resin layer 12 When, the adhesion of hardening resin layer 12 and printing layer reduces.

Measured by the foundation ASME B46.12 on the surface (that is, the surface of printing sheet material 10) of hardening resin layer 12 Arithmetic average roughness (Ra) preferably 0.5~15nm, more preferably 1~10nm.Ra is the surface shape for representing hardening resin layer 12 The index of state, if Ra is in the scope, then mean hydrophobization inorganic fine particles on the surface of hardening resin layer 12 Expose, the surface of hardening resin layer 12 turns into the concavo-convex face (concavo-convex 12a) with appropriateness.Especially if including hydrophobization The Ra on the surface of the hardening resin layer 12 of inorganic fine particles is more than 0.5nm, then can obtain sufficient resistance to adhesive and Printing adaptability.On the other hand, if the Ra on the surface of hardening resin layer 12 is below 15nm, then can maintain well The transparency of printing sheet material 10.

The Ra can by according to ASME B46.12, using be 8nm with radius of curvature, spring constant 42N/m, The scanning probe microscopy for the terminal that resonant frequency is 320kHz, material is single crystalline Si, mensuration region is set to 10 μm of 10 μ m The acquisition of image is carried out, and the image to being obtained is handled, and calculate the Ra on film surface.In addition, as probe, preferably make With Si monocrystalline probes.

Described image processing can also be realized by being connected to the image procossing mechanism of the scanning probe microscopy.Separately Outside, described image processing mechanism can also possess memory and central operation device (CPU, Central Processing Unit).Specifically, using scanning probe microscopy (the Nanoscopel IV and Nanoscope that Veeco companies manufacture IIIa), using Si monocrystalline probe as probe, mode determination is set to rap (Tapping) pattern, and mensuration region is set to 10 10 μm of μ ms and carry out the acquisition of image.Preferably for the image obtained, attached using the scanning probe microscopy Analysis software, carry out once planarizing (Flatten) processing (0 time) and plane fitting (Planefit) processing (XY) After for removing the image procossing of ripple, surface roughness is calculated.

The Ra on the surface of hardening resin layer 12 for example can be inorganic by the hydrophobization contained by hardening resin layer 12 Average grain diameter or the addition of particulate and adjust.Specifically, have that the average grain diameter of hydrophobization inorganic fine particles is bigger, separately Outside, the addition of hydrophobization inorganic fine particles is more, then tendency bigger Ra, there is the average grain diameter of hydrophobization inorganic fine particles It is smaller, in addition, the addition of hydrophobization inorganic fine particles is fewer, then tendency smaller Ra.

In addition, haze value preferably less than 1% of the printing with sheet material 10, total light transmittance preferably more than 87%.If mist Angle value and total light transmittance are in the scope, then printing sheet material 10 can be used as into optical applications well.

Haze value is the value measured by according to JIS K 7136, and total light transmittance is according to measured by JIS K 7361 Value.That is, in the form of the present invention, printing can be measured by the following method with the haze value of sheet material 10：By mist degree Value is defined as the sample using 100mm × 100mm, using the light D65 of CIE standard as light source, by test piece through in light Deviate the percentage through light more than 0.044rad (2.5 degree) from incident light because of scattering.In addition, the haze value is preferred Less than 1.0%, more preferably less than 0.8%.In addition, printing can be carried out by the following method with the total light transmittance of sheet material 10 Measure：Total light transmittance is defined as the sample using 100mm × 100mm, using the light D65 of CIE standard as light source, examination The total ratio through light beam relative to parallel entrance beam integrated using integrating sphere of piece.In addition, the full light passes through Rate preferably more than 87%, more preferably more than 89%.

The haze value or total light transmittance of printing sheet material 10 can by the species of the resin for forming plastic basis material 11, Or form the Ra of the species of the hardening resin of hardening resin layer 12 and the surface of hardening resin layer 12 and adjust.

Printing can for example be manufactured with sheet material 10 using following manner.

First, using as the hydrophobization inorganic fine particles of pigment, hardening resin, solvent and other compositions optionally Mixed, prepare hardening resin layer formation composition.As hardening resin layer formation composition solid content into Divide concentration, relative to the gross mass of hardening resin layer formation composition, preferably 10~60 mass %, more preferably 20~50 matter Measure %.

Then, hardening resin layer formation composition is coated with plastic basis material 11, and makes dried coating film and hardening, thus The printing sheet material 10 that hardening resin layer 12 is formd in plastic basis material 11 can be obtained.

That is, in the form of the present invention, printing preferably includes following steps with the manufacture method of sheet material：Prepare constrictive type Resin bed formation composition；And the hardening resin layer formation obtained in the step is coated on plastics base with composition Material, and obtain the lamination printing sheet material of hardening resin layer on plastic basis material.

As the coating method of hardening resin layer formation composition, such as can enumerate：Use knife type coater, gas Knife coating machine, roll coater, rod coater, gravure coater, micro- gravure coater, rod-type knife type coater, die lip apply The methods of cloth machine, die coater, curtain machine, printing machine.

The formation of hardening resin layer can be fitted with the coating weight of composition according to the thickness of the hardening resin layer 12 of formation Work as setting.

Film, can be by irradiating active energy ray in the case where hardening resin is curable with actinic energy ray resin And harden, in the case where hardening resin is thermmohardening type resin, can be carried out by using heating furnace or infrared lamp etc. Heat and harden.As heating condition, carried out 1~5 minute preferably at 60~100 DEG C, 2 are more preferably carried out at 70~90 DEG C ~3 minutes.

As active energy ray, can enumerate：Ionising radiations such as ultraviolet, electron beam, luminous ray, gamma-rays etc., its In, in terms of the versatility for, preferred ultraviolet.As the light source of ultraviolet, such as can use：High-pressure mercury-vapor lamp, low pressure Mercury vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, carbon arc, xenon arc, electrodeless uv lamp etc..

As electron beam, such as can use by Cockcroft-Wa Erdun (Cockcroft Walton) type, all Deges Pressgang (Van de Graaff) type, resonance variable-pressure, insulating core transformer typ, linear pattern, high-frequency and high-voltage (Dynamitron) The electron beam that the various electron-beam accelerators such as type, high-frequency type are launched.

The hardening carried out by irradiating active energy ray is preferably carried out in the presence of the inert gases such as nitrogen.It is in addition, described The exposure of active energy ray preferably 100~1000mJ/cm², more preferably 150~500mJ/cm²。

Hardening can be carried out with 1 stage, and 2 stages that can be also divided into pre-hardening steps and formal cure step are carried out.

The printing of present embodiment example described above constrictive type of the sheet material 10 due to including hydrophobization inorganic fine particles Resin bed 12 is formed on plastic basis material 11, so resistance to adhesive is excellent.Therefore, can printing when not make printing sheet material and Lithographic plate adhesion and hardening resin layer 12 surface formed printing layer.Its reason considers as follows.

Printing is by making hydrophobization inorganic particles sub-portion with the surface of the printing surface of sheet material 10, i.e. hardening resin layer 12 Ground is divided to expose and turn into male and fomale(M＆F) 12a.Think by with the bumps, the contact surface of hardening resin layer 12 and lithographic plate Product tails off, so as to improve resistance to adhesive.

In addition, if replace hydrophobization inorganic fine particles using hydrophilic inorganic particulate, then constrictive type tree is being made Appropriate male and fomale(M＆F) can not be obtained during lipid layer, and sufficient resistance to adhesive or the transparency can not be obtained.Its reason considers as follows.

If hydrophilic inorganic particulate is added in hardening resin layer formation composition, then in hardening resin In layer formation composition, hydrophilic inorganic particulate aggregates with one another and precipitated, and can not obtain good dispersiveness.Therefore, When the hardening resin layer formation composition that coating only includes the hydrophilic inorganic particulate forms film, can not obtain Appropriate male and fomale(M＆F), i.e. the Ra according to measured by ASME B46.12 does not have a value for turning into 0.5~15nm, hydrophily without Machine particulate will not be uniformly dispersed in hardening resin layer 12.In addition, even if hydrophilic inorganic particulate is in constrictive type tree Disperse well in lipid layer formation composition, particle also aggregates with one another and turns into offspring during coating, average Particle diameter becomes big, so can not similarly obtain appropriate male and fomale(M＆F), hydrophilic inorganic particulate will not be in hardening resin layer 12 In be uniformly dispersed.It is therefore contemplated that sufficient resistance to adhesion can not be also obtained as pigment even with hydrophilic inorganic particulate Property or the transparency.

In addition, in order to show sufficient resistance to adhesion using the poor hydrophilic inorganic particulate of dispersiveness as described above Property, it is necessary to more than the addition of hydrophobization inorganic fine particles, but hardening resin layer hyalinosis obtain it is insufficient.Moreover, recognize It can become big for the bumps on the surface of hardening resin layer, the defects of causing impression when batching printing sheet material.Additionally, it is believed that The bumps on the surface of hardening resin layer can not only become apparent in the case where using hydrophilic inorganic particulate, also can be with grain The average grain diameter of son increases and become apparent.

On the other hand, it is a feature of the present invention that being used as pigment using hydrophobization inorganic fine particles.Hydrophobization inorganic particles Son is because its surface energy is smaller, so the mutual interaction of particulate diminishes, as a result, hydrophobization inorganic fine particles are each other not Easily cohesion, it is dispersed excellent in hardening resin layer formation composition.Moreover, by using average grain diameter be 90nm with Under hydrophobization inorganic fine particles, can obtain light scattering reduce, the transparency it is excellent, and with resistance to adhesive printing piece Material 10.

In the present invention, the pigment that hardening resin layer 12 is included preferably all is hydrophobization inorganic fine particles, but in nothing In the range of the effect for damaging the present invention, hydrophilic inorganic particulate can also be contained.

In addition, if it is the hydrophobization inorganic fine particles that average grain diameter is below 90nm, then constrictive type tree can be suppressed The bumps on the surface of lipid layer 12 become too much, i.e. suppress to be more than 15nm according to the Ra measured by ASME B46.12.Therefore, can be with The defects of obtaining when take-up without impression, and the printing sheet material 10 that the transparency is excellent.

Printing can be printed with sheet material 10 using lithographic plate.I.e., it is possible to as in hardening resin layer Printing layer is formed on 12 and forms the material of decoration sheet.Especially if hardening resin layer 12 has the function of hard conating concurrently, So it is also used as applying sheet material firmly.For the printing process using lithographic plate using printing sheet material 10, i.e. this hair The manufacture method of bright decoration sheet, is addressed below.

The printing of the present invention is not limited to shown in Fig. 1 with sheet material.Such as can also be as shown in Fig. 2 in plastic basis material 11 Easy following layer 13 is set between hardening resin layer 12.

In addition, although Fig. 1, the printing shown in 2 form hardening resin with one side of the sheet material 10 in plastic basis material 11 Layer 12, but for example can also be as shown in figure 3, forming hardening resin layer 12 on the two sides of plastic basis material 11.

[decoration sheet]

Fig. 4 is the sectional view of the composition for the decoration sheet for representing one embodiment of the present invention example.

The decoration sheet 20 of this lamination printing layer on hardening resin layer 12 of the printing shown in Fig. 1 with sheet material 10 21。

Printing layer 21 is mainly applied in for decoration etc..

As printing layer 21, such as can enumerate using printing-ink and the layer of printed pattern, word, photo etc..Print Brush layer 21 can be formed on the whole face of hardening resin layer 12 as shown in Figure 4, can also be formed in hardening resin layer 12 On the face of a part.

Printing layer 21 (polyethylene-based resin, can for example be gathered by printing comprising colouring agent (pigment, dyestuff) and adhesive Acid amides system resin, polyacrylic based resin, polyurethanes system resin, polyvinyl acetal system resin, Amino-Polyester first Acid esters system resin, cellulose esters system resin, alkyd resin) coloring printing ink and formed., can in the case where entering row metal colour developing To use：The particle of the metals such as aluminium, titanium, bronze, the pearlescent pigment that titanium oxide forms is coated with mica.That is, printing layer 21 is excellent Choosing includes colouring agent and adhesive.

The thickness of printing layer 21, i.e. in Fig. 4, the most surface of printing layer 21 is played from the interface of hardening resin layer 12 Preferably 5~50 μm, more preferably 10~40 μm of distance untill (and interface of air)., can be with addition, the thickness is specifically Entered using contact pin type film thickness gauge (the ABS digital display dial gauge ID-C112A with peak-value-holding function that Mitutoyo companies manufacture) Row measure.

Decoration sheet 20 can be printed by using lithographic plate (lithographic plate) to printing with sheet material 10, and (lithographic plate prints Brush) and obtain.Specifically, can be by making lithographic plate and printing be contacted with the hardening resin layer 12 of sheet material 10 to enter Row printing, forms printing layer 21 on hardening resin layer 12 and obtains.

As the material of lithographic plate, as long as there is the effect of the present invention, then be not particularly limited, can be gold Category or plastics, or can be glass.The printing of the present invention is more particularly suitable for using metal lithographic printing with sheet material 10 Version carries out the situation of lithographic printing.

The decoration sheet 20 of present embodiment example described above be to the present invention printing with sheet material 10 implement printing and Into.The present invention printing with sheet material 10 because resistance to adhesive and printing adaptability are excellent, so entering even with lithographic plate Row printing, the printing layer 21 of target can also be formed on hardening resin layer 12.

In addition, the present invention printing with sheet material 10 due to the transparency it is excellent, so using the transparent of its decoration sheet 20 Property is also excellent.

Decoration sheet 20 can be fitted in the use of formed products (adherend) surface.Especially if hardening resin layer 12 Have the function of hard conating concurrently, then be also used as applying sheet material firmly.

[adhesiveness decoration sheet]

In the form of the present invention, at least one side lamination adhesion of the adhesiveness decoration sheet in the decoration sheet Layer.

That is, in the form of the present invention, preferably adhesiveness decoration sheet includes plastic basis material, lamination in the plastics base Hardening resin layer, printing layer and the adhesion layer of at least one side of material, and the lamination plastics base on the adhesion layer Material, on plastic basis material lamination hardening resin layer, and then the lamination printing layer on the hardening resin layer, or On the plastic basis material lamination hardening resin layer, the lamination printing layer on the hardening resin layer, And then the lamination adhesion layer in the printing layer.

Fig. 5 is the sectional view of the composition for the adhesiveness decoration sheet for representing one embodiment of the present invention example.

The adhesiveness decoration sheet 30 of this is sequentially set on the surface of the side of plastic basis material 11 of the decoration sheet 20 shown in Fig. 4 Adhesion layer 31 and releasing sheet 32 are put.

That is, in another form of the present invention, adhesiveness decoration sheet preferably comprises plastic basis material, lamination in the plastics Hardening resin layer, printing layer, adhesion layer and the releasing sheet of at least one side of base material.

Adhesion layer 31 is the layer for making decoration sheet 20 be fitted in adherend.

Adhesion layer 31 preferably comprises adhesive.As the adhesive, such as can use：Natural rubber system adhesive, Synthetic rubber system adhesive, acrylic acid series adhesive, carbamate system adhesive, poly- silica system adhesive etc..Furthermore it is possible to It is any of solvent system, emulsion system, water system.Wherein, in the case of for optical system purposes, with regard to transparency, weather-proof For the viewpoint of property, durability, cost etc., it is further preferred that the adhesive for acrylic acid series solvent system.

In adhesive, other auxiliary agents can also be optionally added.As other auxiliary agents, can enumerate：Tackifier, pH value Regulator, adhesive (tackifier), adhesive, crosslinking agent, adhesive microparticles, defoamer, Antisepticize and mildew preventive, pigment, nothing Machine filler, stabilizer, wetting agent, wetting agent etc..

Preferably 3~500 μm, more preferably 4~300 μm, further preferred 5~150 μm of the thickness of adhesion layer 31.If adhesion The thickness of layer 31 is less than 3 μm, then is difficult to control thickness and easily becomes uneven.On the other hand, if the thickness of adhesion layer 31 More than 500 μm, then there is the situation that undesirable condition is produced in the manufacturing steps such as dry or hardening.In addition, also have in punching etc. The situation of the undesirable conditions such as the spilling of paste is produced in following process.Here, the thickness of so-called adhesion layer 31, such as Fig. 6's In form, untill referring to play the interface of adhesion layer 31 and releasing sheet 32 from the interface of adhesion layer 31 and easy following layer 33 away from From.In addition, in Fig. 7 form, refer to play adhesion layer 31 and releasing sheet 32 from the interface of adhesion layer 31 and printing layer 21 Interface untill distance.The thickness of adhesion layer 31 can use contact pin type film thickness gauge (Mitutoyo companies manufacture have peak Value keeps the ABS digital display dial gauge ID-C112A of function) it is measured.

As releasing sheet 32, such as it can enumerate with releasing sheet base material and be arranged on releasing sheet base material The side of adhesion layer 31 peeling agent layer glass baseplate.

As releasing sheet base material, such as can enumerate：The stationeries such as glazed printing paper, glassine paper, poly terephthalic acid second two Plastic foil class such as ester film or polypropylene screen etc..

As the remover of composition peeling agent layer, such as can use：General add-on type or the poly- silica system of condensed type Remover or the compound containing chain alkyl.It can especially be peeled off well using the higher additive poly silica system of reactivity Agent.

Preferably 20~100 μm of the thickness of releasing sheet 32.

Adhesiveness decoration sheet 30 is, for example, by (below, also will on the surface of the side of plastic basis material 11 of decoration sheet 20 The surface is referred to as " back side of decoration sheet ") it is coated with adhesive and forms adhesion layer 31, and stripping is bonded on the adhesion layer 31 Obtained from sheet material 32.Adhesion layer 31 is formed alternatively, it is also possible to be coated with adhesive on releasing sheet 32, and by the adhesion The back side of layer 31 and decoration sheet 20 is bonded and manufactures adhesiveness decoration sheet 30.

As the coating method of adhesive, can enumerate illustrated above in the explanation of the manufacture method of printing sheet material Various coating methods.

In addition, in the process, after decoration sheet 20 is made to the implementation of printing sheet material 10 printing, in plastic basis material 11 surface forms adhesion layer 31 and releasing sheet 32, but the manufacture method of adhesiveness decoration sheet 30 is not limited to the side Method.

For example, it is also possible to before being printed, formed in advance in printing with the surface of the side of plastic basis material 11 of sheet material 10 viscous Attached layer 31 and releasing sheet 32, and on the hardening resin layer 12 of the printing sheet material with adhesion layer formed printing layer 21 and Manufacture adhesiveness decoration sheet 30.

When using decoration sheet 20, peel off the releasing sheet 32 of adhesiveness decoration sheet 30 and expose adhesion layer 31, And the adhesion layer 31 is fitted in adherend (such as surface of display or touch panel etc.).

The adhesiveness decoration sheet 30 of present embodiment example described above is due to the modeling of the decoration sheet 20 in the present invention The surface of material base material 11 side forms adhesion layer 31, it is possible to the decoration sheet 20 of the present invention is fitted in adherend.

In addition, the adhesiveness decoration sheet 30 shown in Fig. 5 is on adhesion layer 31 due to being provided with releasing sheet 32, so can To be rolled into a roll etc. to be preserved and be transported before using decoration sheet 20.

The adhesiveness decoration sheet of the present invention is not limited to shown in Fig. 5.Such as can also be as shown in fig. 6, in plastics base Easy following layer 33 is set between material 11 and adhesion layer 31.In addition, for example can also be as shown in fig. 7, setting adhesion in printing layer 21 Layer 31 and releasing sheet 32.In addition, for example can also be as shown in figure 8, setting adhesion layer 31 on the two sides of adhesiveness decoration sheet With releasing sheet 32.

[embodiment]

Hereinafter, the present invention is described in detail by embodiment, but the present invention is not limited by following record.

[pigment]

As pigment, following cataloid A~E is used.

Cataloid A：Methyl iso-butyl ketone (MIBK) dispersion liquid (the CIK of silica of the surface through silicic acid anhydride NanoTek companies manufacture, solid content composition 30 mass %, average grain diameter 30nm).

Cataloid B：Methyl iso-butyl ketone (MIBK) dispersion liquid (the daily outputization of silica of the surface through silicic acid anhydride Learn industrial group's manufacture, solid content composition 30 mass %, average grain diameter 10nm).

Cataloid C：Methyl ethyl ketone dispersion (the Nissan Chemical of silica of the surface through silicic acid anhydride Industrial group manufactures, solid content composition 30 mass %, average grain diameter 70nm).

Cataloid D：The methyl iso-butyl ketone (MIBK) dispersion liquid of the not no silica Jing Guo silicic acid anhydride in surface (CIK NanoTek companies manufacture, solid content composition 30 mass %, average grain diameter 30nm).

Cataloid E：Methyl iso-butyl ketone (MIBK) dispersion liquid (the CIK of silica of the surface through silicic acid anhydride NanoTek companies manufacture, solid content composition 15 mass %, average grain diameter 100nm).

In addition, silica of the surface through silicic acid anhydride, i.e. cataloid A, B, C, E are inorganic equivalent to hydrophobization Particulate, cataloid D of the surface not Jing Guo silicic acid anhydride is equivalent to hydrophilic inorganic particulate.

[embodiment 1]

Propenoic methyl carbamate oligomer (trade name Art Resin UN- using 100 mass parts as hardening resin 905, Gen Shang industrial groups manufacture, weight-average molecular weight 40,000~200,000, the mass % of solid content composition 70, and solvent is Toluene), cataloid A and 3 mass parts photopolymerization initiator (trade names of 12 mass parts as pigment IRGACURE184, BASF AG's manufacture) mixed, prepare hardening resin layer formation composition.

The composition of hardening resin layer formation composition is represented in table 1.In addition, hardening resin shown in table 1, The allotment amount (content) of pigment and photopolymerization initiator is the amount (mass parts) to be converted through solid content composition.

Using as plastic basis material PET film (trade name Lumirror U48, Toray companies manufacture, 21cm × 29.7cm, 75 μm of thickness), and the hardening resin layer formation obtained is coated on the plastic basis material with composition bar type On.Thereafter, dried 60 seconds using 80 DEG C of air drier, and then use high-pressure mercury-vapor lamp ultraviolet irradiation machine (EYE GRAPHICS companies manufacture), with exposure intensity 200mW/cm², accumulative light quantity 300mJ/cm²Condition irradiation ultraviolet, in plastics Hardening forms the hardening resin layer that thickness is 3 μm on base material, obtains printing sheet material.

[embodiment 2]

Cataloid A allotment amount is changed to 25 mass parts by 12 mass parts, in addition, utilization and embodiment 1 same mode prepares the hardening resin layer formation composition of the composition shown in table 1.

Obtained hardening resin layer formation composition is used, in addition, utilizes the mode same with embodiment 1 Obtain printing sheet material.

[embodiment 3]

Replace cataloid A using cataloid B, in addition, using with 1 same mode system of embodiment The hardening resin layer formation composition of composition shown in standby table 1.

[embodiment 4]

Replace cataloid A using cataloid C, in addition, using with 1 same mode system of embodiment The hardening resin layer formation composition of composition shown in standby table 1.

[embodiment 5]

Hardening resin layer formation is coated on plastics with composition in a manner of the thickness of hardening resin layer turns into 8 μm On base material, in addition, printing sheet material is obtained using the mode same with embodiment 1.

[embodiment 6]

Use acrylate monomer (trade name ARONIX M-215, the manufacture of East Asia Synesis Company, molecular weight 369, solid content The mass % of composition 100) mixtures of 70 mass parts and the mass parts of methyl ethyl ketone 30 replaces propenoic methyl carbamate oligomer, In addition, the hardening resin layer formation for the composition shown in table 1 being prepared using the mode same with embodiment 1 is combined Thing.

[comparative example 1]

Cataloid A is not used, in addition, is prepared using the mode same with embodiment 1 shown in table 2 The hardening resin layer formation composition of composition.

[comparative example 2]

Replace cataloid A using cataloid D, in addition, using with 1 same mode system of embodiment The hardening resin layer formation composition of composition shown in standby table 2.

[comparative example 3]

Cataloid A is replaced using cataloid E, allotment amount is changed to 24 mass parts by 12 mass parts, In addition, the hardening resin layer formation for the composition shown in table 2 being prepared using the mode same with embodiment 1 is combined Thing.

[comparative example 4]

Hardening resin layer formation is coated on composition in a manner of the thickness of hardening resin layer turns into 0.07 μm On plastic basis material, in addition, printing sheet material is obtained using the mode same with embodiment 1.

[comparative example 5]

The formation of hardening resin layer is coated on modeling with composition in a manner of the thickness of hardening resin layer turns into 20 μm Expect on base material, in addition, printing sheet material is obtained using the mode same with embodiment 1.

[measure, evaluation method]

Dispersiveness is evaluated to the hardening resin layer formation composition obtained in each case.In addition, in each case The printing sheet material obtained, the Ra on the surface of hardening resin layer is measured using method as shown below, and to resistance to Adhesive, the transparency, the adhesion of ink are evaluated.These results are represented in table 1,2.

To the Ra foundation ASME B46.12 on the surface of the hardening resin layer side of printing sheet material, shown using scanning probe Micro mirror Nanoscopel IV and the Nanoscope IIIa of manufacture (Veeco companies), and Si monocrystalline probe is used as probe, Mode determination is set to tapping-mode, mensuration region is set to 10 μm of 10 μ m and carries out the acquisition of image.For what is obtained Image, using the incidental analysis software of the scanning probe microscopy, carry out a planarization process (0 time) and once put down Face process of fitting treatment (XY) calculates surface roughness as after the image procossing for being used for removing ripple.

The formation of hardening resin layer is put into closed vial with composition, and placed 1 day under room temperature (23 DEG C). For the hardening resin layer formation composition after 1 day, the precipitation of the pigment in composition described in visual observations is utilized Degree (dispersiveness), and dispersiveness is evaluated according to following metewand.

A：Pigment does not precipitate.

B：Pigment precipitates.

Will in a manner of the surface of the glass plate (11.5cm × 25cm) of smooth surface and hardening resin layer contact Printing is configured on a glass with sheet material, and wetting whether was produced after 5 seconds using visual observations.Similarly by printing piece Material configure on a glass, and then on the plastic basis material of printing sheet material load 1kg counterweight and printing is applied with sheet material Load, wetting whether was produced after 5 seconds using visual observations, and resistance to adhesive is commented according to following metewand Valency.In addition, produce wetting in the case of, it is meant that printing with sheet-adhesion on a glass.

A：Even if applying 1kg load with sheet material to printing, also without generation wetting.

B：Wetting is not only produced when glass plate configures printing with sheet material, but if applying 1kg's with sheet material to printing Load, just produce wetting.

C：Wetting is just only produced with sheet material in glass plate configuration printing.

Printing is carried out with the haze value of sheet material based on JIS K 7136, the NDH5000 manufactured using Japanese electricity Se companies Measure, and the transparency is evaluated according to following metewand.

A：Haze value is less than 1.00%.

B：Haze value is more than 1.00%.

By 100 mass parts ink (trade name MRX HF-919 are black, the manufacture of ink company of empire) and 5 mass parts curing agents (curing agent of trade name 210, the manufacture of ink company of empire) is mixed and prepares ink A.

In addition by 100 mass parts ink (trade name MRX HF-619 are white, the manufacture of ink company of empire) and the hardening of 5 mass parts Agent (curing agent of trade name 210, the manufacture of ink company of empire) is mixed and prepares ink B.

Screen painting is carried out with the surface of the hardening resin layer of sheet material to printing using ink A, ink B respectively, is used in combination 80 DEG C of dryings 1 hour and the printing layer that thickness is 15 μm is formed on hardening resin layer.

According to JIS K 5600-5-6, gridiron pattern contiguity experiment is carried out using following manner.

Adhesive tape (manufacture of trade name CT28, Nichiban companies) is set to be closely contacted on print in a manner of being compressed from above with finger Adhesive tape is peeled off after brush layer.Will be in 100 lattice, printing layer is all set to 100/ in all grids without situation about peeling off 100, situation about all being peeled off in all grids is set to 0/100, counts printing layer without the grid peeled off, and according to following Metewand the adhesion of ink is evaluated.

A：96/100~100/100

B：50/100~95/100

C：0/100~49/100

Printing loaded with the surface of the hardening resin layer of sheet material lamination PET film (trade name Lumirror U48, Toray companies manufacture, 10cm × 10cm, 50 μm of thickness), with the printing every 100cm of sheet material from the PET film of lamination²Turn into 50kg mode applies loading, and the state on the PET film surface of the lamination after 1 day is confirmed using range estimation, and according to following Metewand impression is evaluated.

A：Depression is not confirmed on a pet film.

B：Depression is confirmed on a pet film.

[table 1]

[table 2]

From table 1,2, in each embodiment prepared hardening resin layer formation composition pigment (hydrophobization without Machine particulate) favorable dispersibility.

In addition, printing sheet material obtained in each embodiment is transparent excellent.

Further, since the printing sheet material obtained in each embodiment is excellent to the resistance to adhesive of glass plate, so display Resistance to adhesive when sening as an envoy to that offscreen version is printed is also excellent.And then because the adhesion with ink is also good, so Also show that with excellent printing adaptability.

In addition, printing sheet material obtained in each embodiment is due in the evaluation of impression, in the PET film of lamination Depression is not confirmed, so no the defects of producing impression when take-up.

On the other hand, the resistance to of the printing sheet material obtained in the comparative example 1 using hydrophobization inorganic fine particles is not glued Even property is poor.

Hardening resin prepared in the comparative example 2 of hydrophobization inorganic fine particles is replaced using hydrophilic inorganic particulate Layer formation composition pigment (hydrophilic inorganic particulate) it is dispersed poor.In addition, the printing sheet material obtained Resistance to adhesive and the transparency are poor, also produce impression.

Although the printing sheet material tool obtained in the comparative example 3 using the larger hydrophobization inorganic fine particles of average grain diameter There is resistance to adhesive, but the transparency is poor, also produces impression.

The resistance to adhesive of printing sheet material obtained in the relatively thin comparative example 4 of the thickness of hardening resin layer to glass plate It is poor.In addition, the adhesion of ink is also poor.

Printing sheet material obtained in the thicker comparative example 5 of the thickness of hardening resin layer it is transparent poor.In addition, The adhesion of ink is also poor.

[explanation of symbol]

10 printing sheet materials

11 plastic basis materials

12 hardening resin layers

12a male and fomale(M＆F)s

13 easy following layers

20 decoration sheets

21 printing layers

30 adhesiveness decoration sheets

31 adhesion layers

32 releasing sheets

33 easy following layers

Claims

1. a kind of printing sheet material, it is the constrictive type for including plastic basis material and lamination at least one side of the plastic basis material The printing sheet material of the planographic printing plate of resin bed, and

The hardening resin layer includes hardening resin and pigment, and the pigment is average grain diameter and table with 5~90nm Inorganic fine particles of the face through silicic acid anhydride, and

In the mass parts of hardening resin 100, the content of the inorganic fine particles through silicic acid anhydride is 3~15 mass Part,

The thickness of the hardening resin layer is 0.1~15 μm,

The inorganic fine particles through silicic acid anhydride will not be imbedded in the hardening resin layer, and one part is described hard The film coated surface of change type resin bed is exposed, and

Arithmetic average roughness (Ra) according to the surface of the hardening resin layer measured by ASME B46.12 for 0.5~ 15nm。

2. a kind of decoration sheet, its lamination print on the hardening resin layer of printing sheet material according to claim 1 Brush layer.

3. a kind of adhesiveness decoration sheet, its at least one side lamination adhesion in decoration sheet according to claim 2 Layer.