JPH0319842A - Soft coating film - Google Patents

Abstract

PURPOSE:To provide a soft coated film excellent in moldability and scratch recovery properties, also excellent in scratch resistance, impact resistance, abrasion resistance and the touch and capable of protecting the surfaces of a plastic product, a metal product and a wood product by providing a resin layer cured by irradiating a composition, which contains one or more kind of urethane acrylate with an mol.wt. of 500-50000 consisting of an isocyanate compound having a specific number of isocyanate groups and a compound having a specific number of hydroxyl groups and radical polymerizable unsaturated groups, with ionizing radiation on a support film. CONSTITUTION:The composition constituting the resin layer in a soft coated film contains urethane acrylate with an mol.wt. of 500-5000 consisting of an isocyanate compound having two or more isocyanate groups and a compound containing 1-4 hydroxyl groups and 1-5 radical polymerizable unsaturated groups. The coating solution 3 of the resin composition is applied to a support film 1 using a coating apparatus 2 and the surface of a mirror surface material 4 is subsequently laminated to the support film 1 so that the surface of a mirror surface state thereof is turned to said film and the formed film is cured by an electron beam irradiator 5 and the mirror surface material 4 is released at last.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a soft coat film that adheres to the surface of articles such as home appliances and furniture, and particularly has excellent shapeability and scratch recovery properties. The present invention relates to a soft coat film that has excellent abrasion resistance, impact resistance, scratch resistance, tactility, etc.

[Problems to be solved by conventional techniques and inventions] In recent years,
Plastic materials, including engineering plastics, are widely used as substitute materials for inorganic materials such as metal materials and glass, taking advantage of their characteristics such as toughness and workability. However, since the surface hardness and scratch resistance are poor, it is necessary to provide a surface protective layer.

Conventional techniques for hardening plastic surfaces include:
Coatings with thermosetting resins such as organosiloxane or melamine or photocuring polyfunctional acrylic resins, or forming thin metal films by vacuum evaporation, sputtering, etc. have been practiced.

However, conventional scratch-resistant surface protective layers using thermosetting resins or photocuring resins lack flexibility and are prone to cracking. Therefore, when a surface protective layer is formed on a curved shaped body or a composite resin film, it is difficult to process the surface into a curved shape, and cracks occur due to bending, so that the surface protective layer is not satisfactory. Furthermore, even when used as a surface protective layer for a flat surface, there are problems in that once scratched, it cannot be recovered or the scratches are noticeable. Furthermore, since the surface protective layer made of a metal thin film is processed in a vacuum system, it has the drawbacks of low productivity and difficulty in processing large shapes.

Therefore, an object of the present invention is to provide excellent formability and scratch recovery properties, as well as excellent scratch resistance, impact resistance, abrasion resistance, and tactility, and to improve the quality of plastic products, metal products, wooden products, etc. An object of the present invention is to provide a soft coat film capable of protecting the surface.

[Means to solve the problem]

As a result of intensive research in view of the above objectives, the present inventors have discovered that by coating a film with a composition containing urethane acrylate with a specific structure and irradiating it with ionizing radiation, the inventors have achieved scratch resistance, impact resistance, and abrasion resistance. The present inventors discovered that a soft coat film with excellent properties such as texture and tactility can be obtained, and came up with the present invention.

That is, the soft coat film of the present invention comprises an isocyanate compound having two or more isocyanate groups,
Contains one or more urethane acrylates with molecules N500 to 50,000 consisting of a compound having 1 to 4 hydroxyl groups and a compound having 1 to 2 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups. or a composition having a molecular weight of 500 to 5, consisting of an isocyanate compound having two or more isocyanate groups and a compound having 1 to 4 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups.
A soft coat film having on a support film a resin layer cured by irradiating ionizing radiation to a composition containing one or more urethane acrylates of 0,000, wherein the glass transition temperature of the cured resin layer is o
℃ or less, and the elongation of the soft coated film after curing is 100% or more.

The surface protective layer formed by curing the above-mentioned composite with ionizing radiation can be obtained by making the urethane acrylate polyfunctional, adjusting the molecular weight and structure of the diol, and adjusting the mixing ratio of the urethane compound and the acrylic monomer. Scratch resistance, flexibility, bendability, etc. can be controlled.

The soft coat film of the present invention will be explained in detail below.

The composition constituting the resin layer in the soft coat film of the present invention comprises an isocyanate compound having two or more isocyanate groups, a compound having 1 to 4 hydroxyl groups,
A compound having a molecular weight of 500 to 50,000 and having 1 to 2 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups.
Contains urethane acrylate with a molecular weight of 500 to 50,000, consisting of an isocyanate compound having two or more isocyanate groups, and a compound having 1 to 4 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups. It is characterized by

Isocyanate compounds that can be used in the present invention are aliphatic or aromatic isocyanate compounds having 2 or more, especially 2 to 3, isocyanate groups in one molecule, such as tetramethylene diisocyanate, hexamethylene diisocyanate, etc. , 2.4-}lylene diisocyanate, 2.6-tolylene diisocyanate, 4.
4. -diphenylmethane diisocyanate, 1,5
-naphthalene diisocyanate, 3,3-dimethyl-4
,4. − Diphenylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate},
1.3-bis(incyanite methyl) cyclohexane, trimethylhexamethylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isocyanates represented by the following formula, etc., singly or in combination of two or more. It can be used as

OCNR, NCO, or Ra-(NCO)s (where R1 is a hydrocarbon group having 4 to 14 carbon atoms,
R2 has an incyanurate or trimethylolpropane skeleton. ) Furthermore, the following isocyanate compounds can also be used.

(A) (C) C}1.0[:ON}I-(CI{.). -NCO 1
13 In order to have particularly weather resistance, inphorone diisocyanate, hexamethylene diisocyanate, hydrogenation 4.
In addition to 4'-diphenylmethane diisocyanate and hydrogenated xylylene diisocyanate, the above (2) to (
) is desirable.

Compounds (monomers) having 1 to 4 hydroxyl groups include methanol, ethanol, propanol, 1,3-butanediol, 1,4-butanediol, trimethylolpropane, pentaerythritol, diglycerol, etc. , polyester brepolymers, polyether brepolymers, polycarbonate brepolymers, polybutadiene brepolymers, and the like having hydroxyl groups.

As polyester prepolymers having 1 to 4 hydroxyl groups, (a) addition reaction products of diol compounds having an aromatic or spiro ring skeleton and lactone compounds or derivatives thereof or epoxy compounds; (b) polybasic acids; and (c) ring-opened polyester compounds derived from Il-like ester compounds, and these may be used alone or in combination of two or more.

Examples of the diol compound having an aromatic or subiro ring skeleton used in the addition reaction raw material of (a) include CH, 0(CLCH20) l, H. etc.

Representative lactone compounds include εcabrolactone and δ-parerolactone.

Further, typical examples of epoxy compounds include ethylene oxide and propylene oxide.

Next, as the polybasic acid used for the condensed biosediment of (0),
For example, saturated polybasic acids such as phthalic acid, isophthalic acid, terephthanoleic acid, adivic acid, succinic acid, and sebacic acid, maleic acid, and fumaric acid. There are unsaturated polybasic acids such as itaconic acid and citraconic acid, and polyols include ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexane glycol.

Examples of polyether prepolymers having 1 to 4 hydroxyl groups include polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, and the like.

Examples of polycarbonate prepolymers having 1 to 4 hydroxyl groups include Plaxel CD-210 (molecular weight 1000) manufactured by Daicel Chemical Industries, Ltd., Blaxel CD-220 (molecular weight 2000) manufactured by Nippon Polyurethane Industries, Ltd., and ON- 983 (molecular weight 10
Examples include polycarbonate diols such as 00).

Examples of the polybutadiene prebolimer include diols having OH groups at both ends of 1,4-polybutadiene and 1,2-polybutadiene.

A compound having 1 to 2 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups binds to the isocyanate group of the isocyanate compound, and easily generates radicals by irradiation with an electron beam, causing a crosslinking reaction. It is a so-called radically polymerizable compound having an unsaturated group. Such radically polymerizable acrylate compounds having a hydroxyl group are ester compounds of acrylic acid or methacrylic acid or derivatives thereof, and have a hydroxyl group, such as hydroxyethyl acrylate,
Hydroxybrobyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxybutyl methacrylate, 4-hydroxycyclohexyl acrylate, 5-hydroxycyclooctyl acrylate, 2-hydroxy-3-phenyloxybrobyl acrylate Including (meth)acrylic acid ester compounds having one polymerizable unsaturated group such as OCR2CH. An ester compound having two polymerizable unsaturated groups represented by 0}1 1 , pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. can be used.

The second urethane acrylate of the present invention has 1 to 4 hydroxyl groups and 1 to 5 hydroxyl groups in the same isocyanate compound as above.
It has a molecular weight of 500 to 50,000 and is obtained by reacting compounds having radically polymerizable unsaturated groups. Examples of the radically polymerizable unsaturated group-containing compound include the following formula: R-{-OCH. C}1(OH)C}I20COCH=
CH, )2 (R is a hydrocarbon residue).

Next, the method for producing the above urethane acrylate will be explained using an example using a diisocyanate and a diol.

The first step using a diisocyanate and a diol having hydroxyl groups at both ends can be represented by the following reaction formula.

2 0CN-R, -NCO + HO-R2-
OH → However, R1 is a hydrocarbon group having 4 to 14 carbon atoms, and R2 is a diol residue.

The reaction temperature in the 1st step is 40-60℃ and the reaction time is 1-4
It's time. The reaction may be carried out without a solvent or in a solvent.

The second step is to react an acrylate compound having a hydroxyl group and a radically polymerizable unsaturated group at the end of the reacted raw material of the first step, and can typically be represented by the following formula.

00 II II OCN-R, -NHCO-R2-OCNII-R, -N
CO+2HD-R, → However, R3 is an acrylate residue (acrylic ester group or methacrylic ester group).

Note that instead of reacting all of the isocyanate residues with the radically polymerizable compound, one end is reacted with a triol such as trimethylolpropane so that three residues of the radically polymerizable compound are contained in one molecule. You can also do it.

The reaction temperature in the second step was 40 to 100 °C, and the reaction time was 2
~6 hours. As in the first step, the step may be carried out without a solvent or in a solvent.

In addition, in the reaction system of the second step, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, penzoquinone, 2.6-
D-t-butyl-p-cresol etc. 100-1000
It is preferable to add about ppm. In addition, triethylamine was added to the reaction system for the purpose of promoting the reaction. Viperazine, triethanolamine, dibutyltin dilaurate,
Stannath octoate, stannath slaurate, dioctyltin dilaurate, etc. can be added.

The urethane acrylate obtained in this way is 500
It is characterized by having a molecular weight of ~50,000. Such a large molecular weight is mainly derived from a compound having a hydroxyl group, and particularly when an aliphatic hydroxyl group-containing compound (diol, etc.) is used, good elongation is exhibited.

The composite used for the soft coat film of the present invention can be obtained from urethane acrylate alone, but if desired, a compound having one or more radically polymerizable unsaturated groups in each molecule (especially acrylic monomer) may be added. species or a mixture of two or more species.

Among the acrylic monomers that can be mixed with urethane acrylate, examples of monofunctional acrylic monomers include methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, and ethoxydiethylene glycol. acrylate, tetrahydrofurfuryl acrylate, phenoxy acrylate, 2-hydroxypropyl acrylate, methoxytriethylene glycol acrylate, acrylic acid dimer nonylphenol ethylene glycol acrylate, 2-hydroxy-3-7 enoxypropyl acrylate, inamyl acrylate, Methoxydipropylene glycol acrylate, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxy Ethyl acid phosphate, 2-hydroxybutyl acrylate, pendyl acrylate, nonylphenol-
10 Acrylic esters such as ethylene glycol acrylate or their corresponding methacrylic esters; Unsaturated carboxamides of acrylamide and methacrylamide; 2-(N, N-dimethylamino>ethyl acrylate, 2-(N, N-dimethylamino) - dimethylamino)
Substituted amino acids of unsaturated acids such as ethyl methacrylate, 2-(N,N-dibenzylamino)ethyl acrylate}, (N,N-dimethylamino)methyl methacrylate, 2-(N,N-jethylamino)probyl acrylate Alcohol esters; N-methylcarbamoyloxyethyl acrylate, N-ethylcarbamoyloxyethyl acrylate, N-butylcarbamoyloxyethyl acrylate, N-phenylcarbamoyloxyethyl acrylate, 2-(N-methyl carbamoyloxy)ethyl acrylate}, carbamoyloxyalkyl acrylates such as 2-carbamoyloxypropyl acrylate, N-vinyl-2-pyrrolidones, and the like.

Further, the polyfunctional acrylic monomer has two or more radically polymerizable unsaturated groups, and polyfunctional (meth)acrylates having two or more (meth)acryloyl groups are particularly preferable.Specific examples include ethylene glycol Di(meth)acrylate, polyethylene glycol di(
meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylic L/-},}!J Methylolpropane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth) Acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol dicrycidyl ether di(
meth)acrylate, polyethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl ether di(meth)acrylate,
Examples include polyfunctional (meth)acrylates such as polypropylene glycol diglycidyl ether di(meth)acrylate, sorbitol tetraglycidyl ether tetra(meth)acrylate, and melamine (meth)acrylate.

The blending ratio of urethane acrylate and acrylic monomer varies depending on the proportion of acrylic component in the urethane acrylate, and it is preferable to blend the two so that the acrylic monomer in the composition is about 5 to 80% by weight.

Note that, as described later, urethane acrylate and acrylic monomer are crosslinked by irradiation with ionizing radiation, so a urethane compound can also be used instead of urethane acrylate. The urethane compound includes an isocyanate compound having two or more isocyanate groups, and one to four isocyanate groups.
A urethane compound obtained by reacting with a compound having hydroxyl groups can be used. The isocyanate compound and hydroxyl group-containing compound used here may be the same as those described above. When using a urethane compound, the blending ratio of the urethane compound and the acrylic monomer is such that the acrylic monomer accounts for about 20 to 80% by weight, as described above.

In order to obtain good tactility, the soft coat film of the present invention has a coating composition of 0.05 to 15 parts by weight per 100 parts by weight of the resin content.
It is preferable to contain one or more tactile feel improvers in parts by weight.

The feel improver may be either liquid or powder, and includes silicone, wax, Teflon powder, surfactant, and the like. However, if the amount added is too large, the adhesion to the support film tends to be poor. The preferred amount added is 0.05 to 10 parts by weight.

The silicones actually used include amino-modified silicones, ether-modified silicones, mercapto-modified silicones, leaf group-containing silicones, Uv or E! There are B-curing silicones, etc., and waxes include polyethylene glycol, polytetramethylene glycol, etc., and silicone powder, wax powder, etc. can also be used.

The resin composition used in the present invention may also contain an ultraviolet absorber or a light stabilizer, if necessary. As ultraviolet absorbers, penzotriazoles, such as 2-(
2-hydroxy-5methylphenyl)penzotriazole, 2-(2-hydroxy-3,5 ditertiary amyl phenyl)penzotriazol, polyethylene glycol 3-[3(penzotriazol-2-yl-5-t) -butyl-4-hydroxyphenyl]propionate and the like.

In addition, the light stabilizer is a hindered amine type, for example, t
lf2-(3.5-di-t-butyl-4-hydroxybenzyl)-2'-n-butylmalonate bis(1,
2, 2. 6-pentamethyl-4-piperidyl)
, bis(1. 2. 2, 6. 6-pentamethyl-4-biperidyl) sebacate, tetrakis(2.
2, 6. 6-tetramethyl-4-biperidyl)
1. 2. 3. Examples include 4-butanetetracarboxylate.

A significant improvement in weather resistance can be obtained by using a UV absorber and a light stabilizer together.

The amount of the ultraviolet absorber added and the amount of the light stabilizer added are 0.01 to 10 parts by weight, respectively, per 100 parts by weight of the resin composition, particularly 0.1 to 2 parts by weight of the ultraviolet absorber and the light stabilizer. It is desirable to add 0.5 to 4 parts by weight at the same time. If the amount added is too small, there will be no effect of improving weather resistance, and if it is too large, adverse effects such as a decrease in curability and adhesion will appear.

The electron beam curable resin composition thus obtained has tackiness before curing. It is important to have tackiness because the physical properties (abrasion resistance, etc.) of the resulting coating film will not be sufficient if there is no tackiness before curing.

Support films used in the present invention include polyester films, polyethylene films, holiflopyrene films, polyvinyl chloride films, polyvinylidene chloride films, polycarbonate films, nylon films, polystyrene films, ethylene-vinyl acetate copolymer films, Use 8BS film, etc.

In the present invention, the supporting film has a thickness of 6 to 500 mm.
Use a material with a diameter of approximately μm. Particularly good effects can be obtained when the thickness of the support film is about 25 to 250 μm.

In the present invention, the thickness of the electron beam cured resin coating is 2 to 150 mm.
It is μm. If it is thinner than 2 μm, the scratch resistance is insufficient. On the other hand, a soft comb film does not tend to curl even if the film thickness increases to a certain extent, but if the film thickness exceeds 150 μm, curing becomes insufficient.

The electron beam cured resin coating film is shaped as follows.

The paint is prepared without a solvent or with the addition of a solvent if necessary.

Usable solvents include alcohols such as methanol, ethanol, imbropanol, methyl cellosolve, and ethyl cellosolve, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ethyl acetate, and butyl acetate. and aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.

As a coating method, a blade coating method, a gravure coating method, a rod coating method, a knife coating method, a reverse roll coating method, an offset gravure coating method, etc. can be used.

The coating film may be directly irradiated with electron beams, but in the case of obtaining a mirror finish, the method disclosed in JP-A-57-22204 is used.

In the method using the apparatus schematically shown in FIG. 1, a coating liquid 3 of the resin composition is applied onto the support film l using the coating apparatus 2.
After coating, the mirror material 4 is laminated with the mirror surface facing the support film 1, the coating film is cured with an electron beam irradiator 5, and finally the mirror material 4 is peeled off. Furthermore, if necessary, preheating may be performed using heaters 6 and 7 before electron beam irradiation, and postheating may be performed using heater 8 after electron beam irradiation.

In FIG. 2, after coating the mirror material 4 with the coating liquid 3 using the coating device 2, the support film 1 is laminated,
The coating film is cured with an electron beam irradiator 5, and finally the cured product is peeled off from the mirror material 4. In this case as well, heater 6 if necessary.
．． Preheating and postheating may be performed according to 7.8.

Mirror materials include metal plates, metal sheets, plastic films, resin coated paper, films, metallized films,
Materials such as metallized paper and glass can be used, but
In particular, as a method that utilizes the low temperature curing characteristics of electron beams,
Preferably, a plastic film having a softening point of 200° C. or less is used.

Furthermore, by using a sheet or panel having a matte surface (for example, a polyethylene terephthalate sheet) instead of a mirror material, a coated surface having a matte surface can also be obtained. In this case, unlike a non-glare layer containing, for example, silica particles, there is no light scattering and it can be made to have a uniform surface unevenness pattern, resulting in a good non-glare layer.

FIG. 3 shows an example of a method for obtaining a matte resin layer having fine irregularities on the surface. After coating the coating liquid 13 on the support film 10, it is pressed onto a forming roll 14 which has fine irregularities in advance. , and in this state, the electron beam is irradiated from the electron beam irradiator 15.

As a result, the coating film 13 is cured, and the fine irregularities of the oval roll 14 are transferred to the surface of the cured coating film. Next, the film is peeled off from the shaping roll (4) using the roll 16, thereby obtaining a matte film having fine irregularities on the surface.

To cure the resin layer obtained in this way, electron beams are emitted from various electron beam accelerators such as Kotscroft-Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high frequency type. 50-1000κeV
, preferably with an energy in the range of 100 to 300 KeV. The amount of electron beam irradiation is 1 to 20 Mrad per shell.

In addition, the soft coat film of the present invention can have a colored layer and/or a metal vapor deposited layer on the support film. These colored layers and/or metallized layers are applied or deposited on the support film in a conventional manner. Thereafter, the resin layer is applied, and a soft coat film is obtained by the method described above.

By having a colored layer and/or a metal vapor deposited layer, a soft coat film can be obtained that exhibits a variety of colors and patterns, and therefore not only functions as a protective layer for articles but also has decorative properties.

Furthermore, it is convenient for the soft coat film of the present invention to be easily attached to articles by providing an adhesive layer on the back side of the support film.

The soft coated film thus obtained is characterized by sufficient elongation. In particular, the cured resin layer in the soft coat film exhibits a glass transition temperature of 0° C. or lower, and therefore has an elongation of 100% or more without causing cracks.

〔Example〕

The present invention will be explained in further detail by the following examples.

Example 1 Using a 500ml separable flask equipped with a heating stirrer and a collapsible cover, 33% of isophorone diisocyanate was prepared. 3 g was placed in a flask, and di-n-butyltin dilaurate was added as a catalyst. Add Ig dropwise, 40°C
The mixture was heated and stirred. 200 g of Plaxel 220AL (Daicel Chemical, molecular weight 2000) was gradually added to the system to prevent a sudden rise in temperature, and the reaction was proceeded.After 2 hours, the reaction temperature was raised to 60°C, and 13 g of hydroxyethyl acrylate was added. 2330Cl in IR spectrum
Stirring was continued until the peak due to the l-' isocyanate group disappeared. After the reaction was almost quantitatively completed, the desired urethane acrylate compound was obtained.

Urethane acrylate compound 4 thus obtained
0 parts by weight, 10 parts by weight of PR-202 (urethane acrylate manufactured by Mitsubishi Kagaku@), diethoxyethyl acrylate (Viscoe manufactured by Osaka Organic Chemical Industry ■ 190)
50 parts by weight and 0.5 parts by weight of Hachik-30 (manufactured by Toa Gosho Chemical Industry Co., Ltd.) as a silicone were added to prepare a coating solution.

This was applied to a thickness of 15 μm on a polyvinyl chloride sheet (manufactured by Sanpo Jushi Kogyo ■) with a thickness of 150 μm using a roll coating method. A matte polyethylene terephthalate film (Teijin ■) was laminated thereon and irradiated with an electron beam of 5 Mrad using a curtain type electron beam irradiation machine (acceleration voltage 180 kV). After the resin was cured, the matte film was peeled off to obtain a soft coat film. The obtained soft coat film was evaluated as follows.

(B) Nail scratch test Scratch the paint film 2 to 3 times with the nail of your index finger (the length of the scratch is about 30mfl+) and observe whether there are significant scratches, scratches that do not recover, or scratches that expose the fabric. do.

○: Not damaged ×: Damaged (b) Bending test: Bend sharply to 180° at 25°C and observe whether cracks occur.

○: Cracks do not occur. ×: Cracks occur.

(2) Adhesiveness test A grid test is conducted according to JISK-5400, and adhesion is evaluated based on the number of remaining pieces.

(Water) Hot water resistance test Observe the surface condition after being immersed in hot water at 50°C for 24 hours.

○: No abnormality ×: Abnormality (f) Humidity resistance test After being left in an atmosphere of 50° C. and 90% RH for 400 hours, the presence or absence of cracking, blistering, peeling, significant discoloration, and change in gloss is observed.

○: No abnormality ×: Abnormality (G) Chemical resistance test 5% acetic acid aqueous solution at 20°C for 96 hours, O.I.
NNail {After being immersed in an aqueous solution for 240 hours and 24 hours in kerosene at 20°C, observe the presence or absence of cracks, blisters, peeling, significant discoloration, and changes in gloss.

○: No abnormality ×: There is an abnormality The results were as shown in Table 2.

Example 2 Similar to Example 1, tolylene diisocyanate 17 4
．． g as a catalyst, di-n-butyltin diuralylate 0
．． 13g of 1,3-butanediol was added dropwise at 40°C. After 2 hours, 60g of isopropyl alcohol was added at 60°C, and 2330c+r was observed in the IR spectrum.
Stirring was continued until the peak due to the isocyanate group ' disappeared, and the reaction was almost quantitatively completed to obtain the desired urethane compound.

To 20 parts by weight of the urethane compound thus obtained, 80 parts by weight of UV-3000B (urethane acrylate manufactured by Japan Gokai Chemical Industry ■), 1.5 parts by weight of AK-30
Parts by weight were added to prepare a coating solution, and a soft coat film was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

Examples 3 to 14 Soft coat films were prepared in the same manner as in Example 1 using each composition shown in Table 1, and the same evaluations were performed.

Similarly, the results are shown in Table 2.

Comparative Example 1 A soft coat film was prepared in the same manner as in Example 1 using the composition shown in Table 1, and the same evaluation was performed. Second
As shown in the table, since the elongation at which cracking occurred was less than 100%, the bending test was X, and a soft coated film with shapeability could not be obtained.

(Note): (1) Urethane acrylate (a) M-5600 manufactured by Nippon Goda Kagaku Kogyo [CH2=CHCOOCH. CH. COO}I Acrylic acid dimer I) Manufactured by Mitsubishi Chemical Corporation (C) Viscoat 190 manufactured by Osaka Organic Chemical Industry Corporation: C}1. =C}IC00(CH
2Cll20). ('21+S (2) Monofunctional acrylic monomer (a) manufactured by Kyoeisha Yushi Kagaku Kogyo ■ THF-A: Tetrahydrofurfuryl acrylate PO-A: Phenoxyethyl acrylate 11
0P-^: 2-hydroxybrobyl acrylate MT
G1^: Methoxytri'ethylene glycol acrylate b) Manufactured by Toa Gosho Chemical Industry ■M-150: N-vinyl-2-pyrrolidone viscoe}158: CH2=CHCOOCH2CH. CH(C
H3) 2(3) Bifunctional acrylic monomer (a) M 215 manufactured by Toa Gosho Chemical Industry Co., Ltd.: CH. CH20H 1 (b) Manufactured by Kyoei Yushi Kagaku Kogyo ■ (e) Manufactured by Osaka Organic Chemical Industry (4) Trifunctional acrylic monomer manufactured by Nippon Gunpowder ■ (C) Manufactured by Nippon Gunpowder ■ "τ・go=2, (5) Texture Improver (a) Silicone (a) Manufactured by Shin-Etsu Chemical @J a+b=3> 00 Manufactured by Toa Goi Kagaku Kogyo (c) Manufactured by Goldschmidt (a) Manufactured by Hodogaya Chemical (2) Toshiba silicone TIJV6000 manufactured by Nippon Unicar ■ L-7001 (b) Teflon powder manufactured by Daikin Industries ■ Lublon L-5 (C) Silicon powder manufactured by Toray Silicon ■ Trefil F-203 (d) Powder (8): 1:1 A mixture of molar ratios.

S-N^U8A5021: Carnauba wax Fluoroslip 511: Fluoroethylene (e) surfactant Emulgen B-210 manufactured by Kao ■ (6): Urethane acrylate produced in Example 1.

(7): Urethane compound produced in Example 2 [Effects of the invention] As detailed above, the soft coat film of the present invention not only has excellent flexibility, flexibility, and scratch recovery ability, but also
It also has excellent properties such as scratch resistance, abrasion resistance, and chemical resistance. Therefore, it is extremely useful as a protective layer for household electrical appliances, furniture, office machines, etc.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of a method for shaping the soft coat film of the present invention, FIG. 2 is a schematic diagram showing another method for shaping the soft coat film of the present invention, and FIG. The figure is a schematic view showing yet another method of forming the soft coat film of the present invention. 1.10 - Support film 2... - Coating device 3.13 - Coating liquid 4... - Shaping material 5, l5 - Electron beam irradiation machine 6.7. '8... Heater (optional use) 14.
・Certain shaped roll with unevenness

Claims (14)

[Claims] (1) An isocyanate compound having 2 or more isocyanate groups, a compound having 1 to 4 hydroxyl groups, and 1
Curing by irradiating a composition containing one or more urethane acrylates with a molecular weight of 500 to 50,000 and a compound having ~2 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups with ionizing radiation. A soft coat film having a cured resin layer on a support film, characterized in that the glass transition temperature of the cured resin layer is 0°C or less, and the elongation of the soft coat film after curing is 100% or more. Soft coated film. (2) A molecular weight of 50 consisting of an isocyanate compound having two or more isocyanate groups and a compound having 1 to 4 hydroxyl groups and 1 to 5 radically polymerizable unsaturated groups.
A soft coat film having, on a support film, a resin layer cured by irradiating a composition containing one or more urethane acrylates of 0 to 50,000 with ionizing radiation, the glass transition of the cured resin layer A soft coat film characterized in that the temperature is 0°C or lower and the elongation of the soft coat film after curing is 100% or higher. (3) The soft coat film according to claim 1 or 2, wherein the content of the urethane acrylate in the composition is 20 to 95% by weight. (4) In the soft coat film according to claim 1 or 2, the composition includes one or more types of the urethane acrylate and one type having one or more radically polymerizable unsaturated groups in one molecule. Or a soft coat film characterized by containing two or more types of acrylic monomers. (5) The soft coat film according to any one of claims 1 to 4, wherein the composition further contains one or more urethane compounds. (6) In the soft coat film according to any one of claims 1 to 5, the composition further comprises 10 resin components.
A soft coat film containing 0.05 to 15 parts by weight of one or more tactile feel improvers per 0 part by weight. (7) In the soft coat film according to any one of claims 1 to 6, the isocyanate compound constituting the urethane acrylate has the following formula: OCNR_1NCO, or R_2-(NCO)_3 (wherein R_1 has a carbon number of 4 to 14 is a hydrocarbon group, and R_2 has an isocyanurate or trimethylolpropane skeleton. (8) The soft coat film according to any one of claims 1 to 7, wherein the surface of the cured resin layer is smooth. (9) The soft coat film according to any one of claims 1 to 7, wherein the surface of the cured resin layer has irregularities. (10) The soft coat film according to any one of claims 1 to 9, wherein the support film has a colored layer. (11) The soft coat film according to any one of claims 1 to 10, wherein the support film has a metal vapor deposited layer. (12) The soft coat film according to any one of claims 1 to 11, wherein the support film is printed. (13) The soft coat film according to any one of claims 1 to 12, further comprising an adhesive layer on the back surface of the support film. (14) One or more urethane compounds consisting of an isocyanate compound having two or more isocyanate groups and a compound having one to four hydroxyl groups, and one or more radically polymerizable inorganic compounds in one molecule. A soft coat film having, on a support film, a resin layer cured by irradiating a composition containing one or more compounds having a saturated group with ionizing radiation, the cured resin layer being glass. A soft coat film having a transition temperature of 0°C or lower and an elongation of 100% or higher after curing.