JPH10278207A - Thermally bondable film and processing material to be covered - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide strong adhesive properties which is harmless to rigid support, particularly to metal plate by providing a hot-melt adhesive layer containing epoxidated material of vinyl aromatic compound-conjugate diene compound block copolymer as a base polymer on one surface of a polyester film. SOLUTION: The thermally bondable film comprises a hot-melt adhesive layer provided on at least one surface of a polyester film. A base polymer of the layer can be used with single epoxidated material of vinyl aromatic compound-conjugate diene compound block copolymer as a main material. 500 pts.wt. of less (except 0 pt.wt.) of tackifier and 500 pts.wt. or less (except 0 pt.wt.) of process oil are mixed with 100 pts.wt. of the base polymer, and hence processability is stabilized. It can be easily handled as the film. And, adhesive properties are stabilized. The bondable film is thermally bonded onto a rigid support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a building material such as an interior material and an exterior material, a member for an office tool, furniture, a kitchen article, a member for an electric / electronic device and a housing, or a member for an automobile, a vehicle, an aircraft, etc. Further, the present invention relates to a heat-bonding film suitable as a mark sheet or the like, and more specifically, has a good heat-bonding property with various rigid supports, and particularly has an excellent adhesive property with a metal material. For example, the present invention relates to a heat-bondable polyester film having a significantly enhanced surface contamination prevention property, and a polyester film-coated product.

[0002]

2. Description of the Related Art As a coated body of a rigid support such as a plywood or a metal plate of a plastic film, a PVC resin film such as a PVC decorative plate or a PVC steel plate has been frequently used.
However, although the PVC-based resin film is excellent in design and cost performance, its surface hardness, oil resistance, solvent resistance, stain resistance, and other durability properties are insufficient,
Since it is a chlorine-containing material, it has a waste disposal problem.

[0003] The thermoplastic polyester film is superior to the PVC resin film in the above points, but the following are examples of conventionally known thermobonding polyester films. In other words, as a conventional technology, a polyester film is coated with an anchor agent (also referred to as an AC agent) such as polyethyleneimine or an alkyl titanate compound as a primer, and polyethylene is extruded or hot-melt coated on the polyester film. As a recent technology, polybutylene terephthalate (P
(BT) A laminated film composed of a film layer and a low melting point PBT-based copolymer layer (JP-A-3-12443) or a laminated film composed of a PBT film layer and a PBT-based resin / nylon polymer blend layer (JP-A-3-136852) ). However, these are films for packaging materials and have poor adhesion to rigid supports, especially metal plates. On the other hand, a modified block copolymer obtained by grafting an unsaturated carboxylic acid to a vinyl aromatic compound-conjugated diene compound-based block copolymer is used for hot melt adhesion between various synthetic resin films containing thermoplastic polyester and an aluminum sheet. It is disclosed that considerable adhesion can be obtained. (JP-A-55-87551)

However, in the case of a graft-modified unsaturated carboxylic acid such as maleic acid or acrylic acid, unreacted monomers remain and thermal dissociation during thermal bonding causes adverse effects on metal supports and hygiene problems. It was a concern.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention is harmless to a rigid support, especially a metal plate,
It is intended to provide a novel heat-bondable polyester film having a strong adhesiveness, a coated product formed by the same, and a surface-treated product having significantly enhanced surface contamination prevention.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a heat bonding method comprising providing a hot melt adhesive layer having a base polymer of an epoxidized vinyl aromatic compound / conjugated diene compound block copolymer on one surface of a polyester film. A polyester film-coated article obtained by thermally bonding a heat-bondable polyester film and a heat-bondable polyester film to a rigid support. Hereinafter, the present invention will be described in detail.

The main resin of the polyester film used in the present invention is a polyalkylene terephthalate resin or a polyalkylene naphthalate resin. Representative examples of these thermoplastic polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-1,4-cyclohexyl dimethylene terephthalate (PCT), and polyethylene-2,6-
Examples include naphthalate (PEN) and polybutylene-2,6-naphthalate (PBN), and particularly preferred are polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

[0008] The polyester is not limited to a homopolymer, but may be a dicarboxylic acid and / or a constituent component of the polyester.
Alternatively, part of the diol may be replaced with another dicarboxylic acid and / or another diol. For example, polyalkylene terephthalate and polyalkylene naphthalate are composed of an aromatic dicarboxylic acid component (terephthalic acid or naphthalenedicarboxylic acid) and an alkylene glycol component (ethylene glycol, 1,4-butanediol, etc.). Examples of the component that can be substituted for part of the acid or phthalenedicarboxylic acid component include dicarboxylic acids or acid anhydrides thereof (for example, maleic acid, maleic anhydride, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Aliphatic dicarboxylic acids such as sebacic acid and dodecanoic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; phthalic acid, phthalic anhydride, isophthalic acid, diphenyl-4,4'-dicarboxylic acid, 3-sulfo acid Aromatic dicarboxylic acids such as isophthalic acid) It is shown. In polyalkylene terephthalate (PET or PBT), part of terephthalic acid is naphthalene-
It may be substituted with 2,6-dicarboxylic acid or the like, and in polyalkylene naphthalate, a part of naphthalenedicarboxylic acid may be substituted with terephthalic acid.
These dicarboxylic acids or acid anhydrides thereof can be used as a mixture of at least one kind or more.

Examples of diols that can partially replace alkylene glycol components (ethylene glycol, 1,4-butanediol, etc.) include, for example, ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, and polyethylene. Glycol, propylene glycol, dipropylene glycol,
Aliphatic diols such as tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentadiol, 1,6-hexanediol, and polytetramethylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
Alicyclic diols such as 2,2-bis (4-hydroxycyclohexyl) propane, and adducts of hydrogenated bisphenol A with alkylene oxides (such as ethylene oxide and propylene oxide); resorcinol, 2,2-bis ( 4-hydroxyphenyl) propane, an adduct of bisphenol A with an alkylene oxide (such as ethylene oxide or propylene oxide) (for example, 2,2′-bis (4-hydroxyethoxyphenyl) propane, 2,2′-bis ( 4-hydroxydiethoxyphenyl) propane, 2,2'-bis (4-
(Hydroxypolyethoxyphenyl) propane, 2,2 ′
-Bis (4-hydroxypropoxyphenyl) propane, 2,2'-bis (4-hydroxydipropoxyphenyl) propane, 2,2'-bis (4-hydroxypolypropoxyphenyl) propane, etc.) as an example. Is done. These diols can be used as a mixture of at least one kind.

A part of the terephthalic acid, naphthalene carboxylic acid component and alkylene glycol component may be substituted with hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids such as glycolic acid and oxypropionic acid; and aromatic hydroxycarboxylic acids such as hydroxybenzoic acid. One or more of them can be used in combination.

The molecular weight of the above polyester resin is, for example, about 5,000 to 1,000,000, which is a weight average molecular weight.
0, preferably about 10,000 to 500,000, and often about 15,000 to 100,000. The intrinsic viscosity of polyester resin is 25 ± 1 ℃
When the solvent o-chlorophenol is used in at least about 0.5 dl / g or more, preferably 0.75 to 2.5 d
It is about 1 / g. The polyester for the polyester film used in the present invention may be used alone or as a blend of two or more.

The polyester film used in the present invention comprises:
Either unstretched polyester or stretched polyester may be used, but stretched polyester films excellent in mechanical properties and the like (for example, biaxially stretched polyethylene terephthalate film or polyethylene naphthalate film) are suitable. When a polybutylene terephthalate film or a polybutylene naphthalate film having excellent heat resistance and mechanical properties is used, it is not always necessary to stretch.

The polyester film used in the present invention comprises:
A single-layer structure or a multi-layer structure may be used. In the case of a multi-layer structure, for example, a PET / PBT composite film or the like is used. Lamination forming method is extrusion lamination method, dry lamination method,
Coextrusion melting, an extrusion method and the like are used.

The epoxidized vinyl aromatic compound-conjugated diene compound block copolymer (hereinafter abbreviated as epoxidized block copolymer) used as the base polymer of the hot melt adhesive layer in the present invention will be described. . The vinyl aromatic compound-conjugated diene compound-based block copolymer (hereinafter, abbreviated as block copolymer), which is a raw material polymer for synthesizing the epoxidized product, means the following two types of block copolymers. I do.

One of them is composed of a polymer block mainly composed of a vinyl aromatic compound (hereinafter represented by A) and a polymerization pair mainly composed of a conjugated diene compound (hereinafter represented by B). A block copolymer (hereinafter simply abbreviated as block copolymer), and the other is a block copolymer having such a structure, which has an unsaturated bond (-C = C) in a B block. Partially hydrogenated (added with hydrogen) (hereinafter abbreviated as partially hydrogenated block copolymer) is meant.

As the vinyl aromatic compound constituting the block polymer, for example, styrene, α-methylstyrene,
One or more of vinyl toluene, p-tertiary butyl styrene, divinyl benzene, p-methyl styrene, 1,1-diphenyl styrene and the like can be selected, and styrene is particularly preferred.

Examples of the conjugated diene compound constituting the block polymer include butadiene, isoprene,
One of 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, and the like;
Alternatively, two or more types are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

The weight percent ratio of the vinyl aromatic compound constituting the block copolymer to the conjugated diene compound is 5/95 to 70.
/ 30, and particularly preferably 10/90 to 60/40. The number average molecular weight of the block copolymer is 5,000 to 6
00,000, preferably 10,000-500,00
0 and the molecular weight distribution [weight average molecular weight (Mw)]
(Mw / Mn)] and the number average molecular weight (Mn) is 10
It is as follows. The molecular structure of the block polymer may be linear, branched, radial, or any combination thereof.

As an example of the molecular structure of the block polymer, A
-BA, BABA, (AB-) ₄ Si, A-
BABA and the like.

As a method for producing the block polymer, any production method having the above-mentioned structure can be used. For example, Japanese Patent Publication No. 40-23798, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423, Japanese Patent Application No. 49-105970, Japanese Patent Application No. 50-27094,
JP-B-46-32415, JP-A-59-166518
No., JP-B-49-36957, JP-B-43-1797
9, JP-B-46-32415, JP-B-56-289
No. 25, a vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst or the like. Further, as a method for producing a partially hydrogenated block copolymer, for example,
According to the method described in JP-B-42-8704, JP-B-43-6636, or JP-A-59-133203, hydrogen was added in an inert solvent in the presence of a hydrogenation catalyst to obtain a partial solution. A hydrogenated block copolymer can be synthesized.

The epoxidized block copolymer of the present invention is obtained by reacting the above block copolymer and / or partially hydrogenated block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. Can be obtained by epoxidation. The peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Of these, peracetic acid is a preferred epoxidizing agent because it is industrially produced in large quantities, is available at low cost, and has high stability.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

At the time of epoxidation, a catalyst can be used if necessary. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. Also,
In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or polybutenehexacarbonyl in combination with tert-butyl hydroperoxide. .

There is no strict regulation on the amount of epoxidizing agent, and the optimum amount in each case depends on the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, etc. Determined by variable factors.

The inert solvent for the epoxidizing agent can be used for the purpose of lowering the viscosity of the raw material, stabilizing the epoxidizing agent by dilution, etc. In the case of peracetic acid, aromatic compounds, ethers, Esters and the like can be used. Particularly preferred solvents are hexane, cyclohexane,
Toluene, benzene, ethyl acetate, carbon tetrachloride, and chloroform. There is no strict regulation on the epoxidation reaction conditions. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. For example, for peracetic acid,
70 ° C. is preferred. If it is less than 0 ° C., the reaction is slow, and if it exceeds 70 ° C., peracetic acid decomposition occurs. In the case of tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetate, which is an example of hydroperoxide, the temperature is preferably from 20C to 150C for the same reason. No special operation of the reaction mixture is required, for example, the mixture may be stirred for 2 to 10 hours. The obtained epoxidized block copolymer can be isolated by an appropriate method, for example, a method of precipitating with a poor solvent, a method of throwing the polymer into hot water with stirring and distilling off the solvent, a direct desolvation method, and the like. Can be done with

For more detailed synthesis conditions of the epoxidized block copolymer, see JP-A-6-279530.
No.

The resin composition constituting the hot-melt adhesive layer used in the heat-bondable film of the present invention can be composed of a base polymer alone such as an epoxidized block copolymer alone as a main material. By blending the agent and the process oil, the processability is stabilized and the handling as a film becomes easy. In addition, the adhesiveness is stabilized.

Examples of the tackifier to be used for the compounding include coumarone resins such as coumarone and indene tree; p-tert-butylphenol / acetylene resin, phenol / formaldehyde resin, terpene / phenol resin, polyterpene resin, xylene / formaldehyde resin and the like. Phenol,
Terpene resin; synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, aliphatic / alicyclic petroleum resin, aliphatic / aromatic petroleum resin, Saturated hydrocarbon (olefin / diolefin) polymer, hydrogenated hydrocarbon resin, hydrocarbon tackifying resin, polybutene, atactic polypropylene, liquid polybutadiene, cis-1,4-polyisoprene rubber, hydrogenated poly Petroleum hydrocarbon resins such as isoprene rubber and modified liquid polyisoprene rubber; pentaerythritol ester of rosin, glycerol ester of rosin, hydrogenated rosin, highly hydrogenated rosin ester, methyl ester of hydrogenated rosin, Triethylene glycol ester of hydrogenated rosin, pentaerythritol of hydrogenated rosin Rosin derivatives such as rosin ester, hydrogenated rosin ester, high-melting ester resin, polymerized rosin, resinate zinc, cured rosin, rosin-based tackifier; turpentine-based tackifier, synthetic resin and phthalate ester Examples include co-condensation products, specially prepared products, nonionic activators, and other tackifiers such as rubber-metal adhesives.

Examples of the process oil to be blended include petroleum softeners such as paraffin-based process oils, naphthene-based process oils, and aromatic-based process oils as mineral oil-based softeners, process oils, special process oils, and the like. Co-oligomer of ethylene and α-olefin, paraffin wax, liquid paraffin, white oil (white oil), petrolatum, petroleum sulfonate, Gilsonite, petroleum asphalt, petroleum resin, cumarone indene resin and the like. Furthermore, castor oil cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, rosin, pine oil, dipentene, softeners including pine tar, tall oil, vegetable oil such as refined tall oil Sub softeners; sub- (factis); fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, myristic acid, barium stearate and calcium stearate; specially prepared softeners.

These can be appropriately selected according to the application, but those of a variety that can be blended with the diene rubber can generally be suitably used in the present invention. As the tackifier, a terpene-based hydrocarbon resin is preferable, and an aromatic-modified terpene light hydrocarbon resin is particularly preferable. As the process oil, a mineral-based process oil is preferable, and a naphthene-based process oil is particularly preferable. Further, two or more kinds of pressure-sensitive adhesives and process oils may be blended respectively.

Next, the formulation of the resin composition constituting the hot melt adhesive layer will be described. Base polymer 100
500 parts by weight or less of the tackifier with respect to parts by weight (hereinafter, parts by weight indicate the blending amount with respect to the base polymer 100 and are indicated by PHR), and 5 parts by weight of the process oil.
00P. H. It is a hot melt adhesive resin composition blended in a ratio of R or less. Preferably the tackifier is 20
~ 300P. H. R. , Process oil 20-300
P. H. R. It is a resin composition compounded with. More preferably, the tackifier is 50 to 200 P.S. H. R. , Process oil 50-200P. H. R. It is a resin composition that is blended.

Further, in the present invention, various antioxidants can be blended to further enhance the stability of the hot melt adhesive resin composition, especially the thermal stability. These stabilizers are described in "Practical Handbook of Additives for Plastics and Rubber" (published in 1970 by Chemical Industry Co., Ltd.)
P. 147-304, p. 1041 to 1054. Stabilizers commonly used in thermoplastic resins, for example, 2,6-di-t-butyl-p-cresol, 2,2-methylbis (4-methyl6-t-4butylphenol), 4,4-butylidenebis (3-methyl-
6-tbutylphenol), 4,4-thiobis (3-
Methyl-6-t-butylphenol), 2,2 thiobis (4-methyl 6-t-butylphenol), stearyl-
β- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, tetrakis [methylene-3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate] methane, triethylene glycol, bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-triethyl-2,4,6 tris (3,5-di -T-butyl-4-hydroxybenzyl) benzene, 1,1,1
Phenolic antioxidants such as 3-2 methyl-5-t-butylphenol) butane; phenyl-α-naphthylamine, phenyl-β-naphthylamine, N-phenyl-
N'-cyclohexyl, p-phenylenediamine, N-
Amine stabilizers such as isopropyl-N'-phenyl-p-phenylenediamine, phosphorus represented by triisodecyl phosphate, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphate, etc. System stabilizer, 2, 2'-thiobis (4-methyl-6-t-
Butylphenol), a sulfur-containing stabilizer represented by 2,
Hydroquinone stabilizers represented by 5-di-t-amylhydroquinone can be suitably used. The amount of the stabilizer is preferably from 0 to 5 parts by weight based on 100 parts by weight of the resin composition constituting the hot melt adhesive layer in the present invention. When the amount of these stabilizers is 10
If the amount exceeds 5 parts by weight with respect to 0 parts by weight, heat creep resistance is impaired, and the cost becomes high economically. Further, these stabilizers may be used alone or in combination of two or more kinds, and when used in combination of two or more kinds, the thermal stability tends to be further improved.

Further, other additives such as pigments, dyes, inorganic fillers, fragrances and ultraviolet rays may be added to the resin composition constituting the hot melt adhesive layer used in the present invention within a range not to impair the object of the present invention. An absorbent, oil or the like may be added. Further, for example, a metal soap-based lubricant or an anti-blocking agent can be added within a range that does not inhibit the hot melt adhesiveness of the composition.

The resin composition constituting the hot melt adhesive layer in the present invention can be prepared by a conventional method, for example, by heating and melting and mixing the components. In many cases, the heat melting and mixing are usually performed under normal pressure, but may be performed under increased pressure or reduced pressure. The heat melting and mixing may be affected by the high melting point component, but is usually in the range of about 70 to 300 ° C, preferably about 80 to 250 ° C. The apparatus for heat melting and mixing is not limited as long as heating and mixing are possible. Usually, a tank with a stirrer is often used. In addition, intelligent mixer, Banbury mixer,
A super mixer, Henschel mixer or the like can be used.

As another mixing method, each component may be dissolved or dispersed in an organic solvent to prepare a solution or dispersion. The organic solvent is not particularly limited, but preferably dissolves the base polymer, and generally, toluene, xylene, ethyl acetate, methyl ethyl ketone, tetrahydrofuran and the like are suitable.

The heat-bondable polyester film of the present invention is provided with a hot-melt adhesive layer made of the above resin composition on one side of a predetermined polyester film. All methods can be applied. For example, if the composition is a solution or dispersion having a relatively low viscosity, gravure coating, reverse coating, and the like are preferable.If the composition is a relatively high viscosity fluid or hot melt composition, doctor blade coating, calendaring, etc. Roll coating, extrusion or hot melt coating, laminating and the like are preferred.

In the present invention, the rigid support used includes a metal base material such as steel, stainless steel, aluminum, brass and copper, a wooden plate, a plywood, a cement processed product, a glass plate, a ceramic plate, and a hard plastic. It is a non-flexible support such as a plate, and in particular, a steel plate, a stainless plate, an aluminum plate, or the like is preferable in consideration of workability, mechanical strength, durability, and the like.

Next, when the heat-bonded polyester is heat-bonded to the rigid support to produce the polyester-coated body of the present invention, a known lamination method by hot melt bonding, for example, using a hot plate press or a laminator is used. And can be manufactured. In the heat-bondable polyester-coated body of the present invention, the adhesive strength of the hot-melt adhesive layer to the rigid support is preferably not less than a T-shaped peel strength of 0.5 kg / 25 mm width.

The heat-bondable polyester film of the present invention or a film-coated product obtained by thermally bonding the same to a rigid support, as it is, has good stain resistance due to the excellent physical and chemical properties of the polyester film surface. Although the present invention exhibits durability, the present invention further provides a means for further enhancing its characteristics.

That is, another constitution of the present invention is the above-mentioned heat-bonding polyester or heat-bonding film having a cured clear coat on the surface of the polyester-coated product of the present invention.

The curable clear coat used for the heat-bonding film or the coated product having such a structure is a coating agent mainly composed of a melamine resin, a fluorine resin, a polyurethane resin, a polysiloxane resin or a modified resin thereof. Can be used. We have:
As a result of various studies on the application of various coating agents, firstly, it was found that a coating agent mainly composed of an organopolysiloxane and / or an acryl-modified organopolysiloxane is more suitable for the present invention in terms of processability and physical properties. I found it.

As such a polysiloxane resin, a suitable combination of the following heat-curable organochlorosilanes (a) RSix ₃ , R ₂ SiX ₂ ,
_{(B) RSiX 3, R'SiX 3} , ( wherein, R, R ', X
Each represents CH ₃ , C ₆ H ₅ , or Cl), and an organopolysiloxane (silicone varnish) having a three-dimensional network structure obtained by polycondensation, or an acrylic-modified polysiloxane or a mixture thereof is obtained. can give.

Examples of the organopolysiloxane include a compound represented by the general formula: Me ₃ SiO (Me ₂ SiO) _l (MeHSiO) _m [(M
e or φ) SiO] _n SiMe ₃ , CH ₂ ＣＨCHMe ₂ SiO (Me ₂ SiO) ₁ SiMe ₂ C
H = CH ₂ , CH ₂ ＣＨCHMe ₂ SiO (Me ₂ SiO) ₁ (CH ₂ ＣC
HMeSiO) _m [(Me or φ) SiO] _n SiMe
₂ CH = CH ₂ , (MeSiO _3/2 ) _l (φSiO _3/2 ) _l ′ (Me ₂ SiO
_2/2 ) _m '(MeφSiO _2/2 ) _m ''(O _1/2 H) _n , (Me ₃ SiO _1/2 ) l (Me2SiO _2/2 ) m (SiO _4/4 ) n (O _{1 / 2} H) n ', wherein Me represents CH ₃ and φ represents C ₆ H ₅ .

Examples of the acryl-modified polysiloxane include those obtained by condensation of a thermosetting acrylic resin having an alkylol group (—ROH) as a functional group with an organosiloxanol or an organosiloxane; A mixture of a drying acrylic resin and an organopolysiloxane can be used. The above-mentioned organopolysiloxane resin used in the present invention has sufficient stain resistance and protective film in a dry coating thickness of 1 to 50 μm, preferably 3 to 10 μm as a coating thickness on a plastic film substrate. The effect is exhibited. As a coating method, a conventional method can be used as it is. That is, a roll coater, a reverse roll coater, an air knife coater, a blade coater, a spray, or the like can be used. In these methods, the applied coating film is usually 1
The material is dried by heating at 90 ° C. for 0.5 hour, and thereafter is annealed (heat treated) at a low temperature for a long time, and is thereafter cured.

The above-mentioned organopolysiloxane resins are usually cured by heating or irradiation with light. If necessary, a fatty acid salt such as zinc, lead, cobalt, tin, iron or the like may be added as a curing accelerator to cure the resin. You can also speed up.
Furthermore, as a curable clear coat suitable for the present invention, by using a polyfunctional urethane acrylate-based active energy ray-curable resin composition as described in detail below, excellent stain resistance and easy removal properties can be obtained. Can be

Polyfunctional urethane acryl used in the present invention
The active energy ray-curable resin composition has the following general formula (In the formula, n represents an integer of 3 to 5, and R ¹ has 5 to 5 carbon atoms.
10 alcohol - R ² is Le residue is a hydrogen atom or a methyl group, R ³ organic diisocyanate - DOO a residue X compound 40-60 wt% and the following general represented by represents a urethane bond) Formula (II) (Wherein, R ¹ is an alcohol residue having 5 to 10 carbon atoms, R ² is a hydrogen atom or a methyl group, and n is 3 to 6
With respect to 100 parts by weight of a composition comprising 40 to 60% by weight of a compound represented by the following general formula: (Wherein n is an integer of 10 to 25, m1 and m2 represent 0 or an integer of 1 to 5, and R represents a methyl group or a hydrogen atom).
1 mol and a polyisoanate component represented by the following general formula (Wherein, R represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a substituted phenylene group) represented by the following formula: , Below, general formula (Wherein, R ¹ is an alcohol residue having at least one hydroxyl group and having 5 to 10 carbon atoms, R ² is a hydrogen atom or a methyl group, and n represents an integer of 3 to 5). A composition comprising 0.1 to 10 parts by weight of a polyfunctional urethane acrylate obtained by reacting a compound represented by the formula (I).

When this composition is used, it is possible to obtain a hard cured coating film having good curability to active energy rays, abrasion resistance and surface smoothness.

A mixture of the compounds represented by the general formulas (I) and (II) can be produced by the following reaction steps. That is, based on 1 mol of the organic diisocyanate,
It can be obtained by charging a compound having a hydroxyl group and an acryloyl group or a methacryloyl group in a molecule in excess of the theoretical amount.

The mixing ratio of the compounds represented by the general formulas (I) and (II) is most preferably in the range of 40 to 60% by weight of the compound represented by the general formula (I) based on the total weight of both. . If it is less than 40% by weight, the cured product is not sufficiently flexible, and if it exceeds 60% by weight, the surface hardness of the cured product is not sufficient, which is not preferable as a hard coat material.

Specific examples of the compound having a hydroxyl group and an acryloyl group or a methacryloyl group in the molecule represented by the general formula (II) used in this reaction include pentaerythritol tri (meth) acrylate, pentaerythritol Erythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Is mentioned.

This reaction is carried out in a dry air atmosphere at 50 to 8
Perform in a temperature range of 0 ° C. Further, in this reaction, it is preferable to use a catalyst. Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organic tin compounds such as tin octylate, dibutyl tin oxide, and cyptyl tin dilaurate;
Further, stannous chloride, stannous bromide, stannous iodide and the like can be used. The added amount of these catalysts is 10 to 10,000 PPM based on the total charged amount.

A radical polymerization inhibitor can be used to suppress the radical polymerization of the acryloyl group. Examples of the radical polymerization inhibitor include hydroquinone monomethyl ether, dt-butyl hydroquinone, p-
t-butyl catechol, phenothiazine and the like. The addition amount is 10 to 10,000 based on the whole charged amount.
PPM is appropriate. The urethane acrylate mixture obtained in this reaction has a reaction yield of almost 100%.
No special production process is required.

The organic diisocyanate used in the present invention includes m-phenylene diisocyanate, p-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylmethane-4,
4'-diisocyanate, 3,3'-dimethyl-4,
Aromatic diisocyanate such as 4'-biphenylene diisocyanate, ethane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate , Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate
And aliphatic diisocyanates. Urethane acrylate having a polydimethylsiloxane skeleton and an isocyanurate skeleton in the main chain can be produced by the following two-step reaction process. In the first reaction, polydimethylsiloxanediol 1 having a hydroxyl group at a molecular terminal is used.
Polyisocyanate having mole and isocyanurate skeleton
Isocyanate group 2 at the molecular end by reaction with
This is a step of obtaining a urethane prepolymer having moles.

This reaction is generally carried out in the above (III) and (I)
Using a compound represented by V), the following reaction formula (However, R _X represents a residue of polydimethylsiloxane diol represented by the general formula (III), and R has 1 to 1 carbon atoms.)
0 alkyl group, phenylene group, substituted phenylene group,
R ^(IV) represents a residue excluding all RNCO groups in the compound represented by the general formula (IV))

Specific examples of the compound represented by formula (IV) used in this reaction include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate. Nate,
Trimers of 4,4'-methylenebis (cyclohexyl diisocyanate), isophorone diisocyanate, and trimethylhexamethylene diisocyanate are exemplified.

The urethane prepolymer at the isocyanate end obtained at this stage has extremely poor solubility in organic solvents and cannot be dissolved in many organic solvents which are usually used industrially. However, it shows very good solubility for some ketones, especially acetone. Therefore, during the reaction, the polyisocyanate having the isocyanurate skeleton is dissolved in acetone beforehand,
The reaction is a condition for obtaining a urethane acrylate solution having a uniform composition.

This reaction is carried out under a nitrogen atmosphere at room temperature to 50 ° C.
The temperature range is as follows. This reaction preferably uses a catalyst. Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; and organic tin compounds such as tin octylate, dibutyl tin oxide, and cyptyl tin dilaurate. , Stannous chloride, stannous bromide, stannous iodide and the like can be used.

The addition amount of these catalysts is 10 to 10,000 PPM with respect to the total charged amount. An acrylate compound having a hydroxyl group at the molecular terminal and having an acryloyl group which is a radically polymerizable unsaturated group is added to 1 mol of the urethane acrylate prepolymer having an isocyanate group at both ends of the molecule thus formed. The reaction to be performed is generally the following reaction formula (Where Rx represents a residue of polydimethylsiloxane diol represented by the general formula (III), and R has 1 to 1 carbon atoms)
R ^(IV) represents an alkyl group, a phenylene group, or a substituted phenylene group of 10; R ^(IV) represents a residue excluding three RNCO groups in the compound represented by the general formula (IV)) .

This reaction is basically a urethanization reaction similar to the step of obtaining a urethane prepolymer.

The amount of the acrylate compound having a hydroxyl group at the molecular terminal and having an acryloyl group which is a radical polymerizable unsaturated group is determined based on the isocyanate compound at both molecular terminals.
It is preferable to use an excess amount of 5 to 7 moles based on 1 mole of the urethane acrylate prepolymer having a hydroxyl group. The reason for this is that the isocyanate group remaining in the urethane prepolymer has extremely poor reactivity with the hydroxyl group, and the urethane-forming reaction does not proceed unless the reaction is carried out under an excessive amount of the hydroxyl group concentration.

This addition reaction is carried out in a dry air atmosphere at a reaction temperature of room temperature to 50 ° C. It is preferable to use a catalyst for this reaction. Examples of the catalyst include organotitanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organotin compounds such as tin octylate, dibutyltin oxide, and sibutyltin dilaurate; , Stannous chloride, stannous bromide,
Stannous iodide or the like can be used. The amount of the catalyst used is 10 to 10,000 PPM with respect to the total charge. Further, a radical polymerization inhibitor can be used to suppress the radical polymerization of the acryloyl group.

Examples of the radical polymerization inhibitor include hydroquinone monomethyl ether, dt-butyl hydroquinone, pt-butyl catechol, and phenothiazine. The addition amount is 10 to 1 with respect to the total charged amount.
000 PPM is a suitable amount. Since the reaction yield of the urethane acrylate obtained by this reaction is almost 100%, no special production step is required.

The polyfunctional urethane acrylate having a polydimethylsiloxane skeleton and an isocyanurate skeleton in the main chain thus obtained is mixed with another polyfunctional acrylate compound to form a photocurable resin composition. When it is used as a cured product, it easily copolymerizes with other polyfunctional acrylates and becomes a constituent of a cured film, which has the effect of improving the abrasion resistance of the coating film.
Further, since the phenomenon of migration from the inside of the cured film is suppressed, it is possible to contribute to the improvement of the surface smoothness of the cured film, unlike the silicone-based additive generally used. The polyfunctional urethane acrylate obtained in the present invention has a polydimethylsiloxane skeleton in the main chain and, at the same time, has an isocyanurate skeleton, so that it imparts planar smoothness and scratch resistance to the urethane acrylate. be able to.

Further, since there are a plurality of acryloyl groups and methacryloyl groups having high curability at the molecular terminals, good curability to active energy rays can be provided.

In the polydimethylsiloxanediol used in the present invention, n is 1 in the composition represented by the general formula (III).
The range of 0 to 25 is most preferred. When n is less than 10, the characteristics of the polydimethylsiloxane skeleton such as scratch resistance and surface smoothness do not appear, and when n exceeds 25, a sufficient crosslinking density cannot be obtained, which is not preferable.

The active energy ray-curable resin composition of the present invention is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the compound represented by the formula (I). When the amount is less than 0.1 part by weight, the effect as an additive does not appear, and when the amount exceeds 10 parts by weight, the surface smoothness of the effect material is adversely affected.

When the ultraviolet-curable resin composition of the present invention is photocured by irradiating it with ultraviolet light, a photopolymerization initiator can be used, but any photopolymerization initiator can be used as long as it initiates and accelerates the polymerization reaction of acryloyl groups. There is no limitation, and known compounds can be used. Specifically, as a photopolymerization initiator,
2,2-hydroxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, anthraquinone, triphenylamine, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone,
N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone, benzoinpropyl ether, acetophenone diethylketal, benzoinnetylether, benzyldimethylketal, 1- (4- Isopropylphenyl) -2-hydroxy-2-methylpropane-
Examples thereof include 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other thioxanthone compounds, and one or more of these compounds can be used.

The use amount of the photopolymerization initiator is preferably 1 to 15 parts by weight, more preferably 1 to 5 parts by weight, based on the photocurable resin composition of the present invention.

In the present invention, the other side of the heat-bondable polyester film, that is, the hot-melt adhesive layer
As a method of applying a curable clear coat on the surface opposite to the film surface, there are various known coating methods as described above.As a processing step, a hot melt adhesive layer is previously formed on a surface-treated polyester film. There is a step of providing and a step of providing a curable clear coat on the polyester film provided with the hot melt adhesive layer first. In the case where the curable clear coat requires considerable heat treatment, the former step is generally preferable. In the case of a polyester film-coated product, a coated product obtained by thermally bonding a heat-bondable film and a support. For
There are two processing steps: surface treatment of a curable clear coat or thermal bonding of a heat-bondable polyester film that has been surface-treated in advance to a support. It is necessary to set in consideration of the curing conditions and the thermal bonding conditions of the film and the support, especially the heating conditions of both, and the thermal deformability of the film support. In addition, when the curing reaction of the curable clear coat is performed without heating at a high temperature in any case of the heat bonding film and the coated processed body, for example, in the case of UV curing, EB curing, etc. You may take it. Next, the configuration and effect of the present invention will be described in more detail with reference to examples. However, it is apparent that the technical scope of the present invention is not limited thereto.

[0070]

【Example】

1 Raw materials 1-1 Polyester film PET: Diafoil Hoechst Co., Ltd. Product name:
"T100E 25μ" PBT: Daicel Chemical Industries, Ltd. product name "Thermolite ES03 25μ"

1-2 Hot Melt Adhesive Layer (Hot Melt Adhesive Resin Composition) Epoxidized Block Copolymer: A product of Daicel Chemical Industries, Ltd., trade name "Epofriend A"
1020 "-Block copolymer: Styrene-butadiene-styrene resin manufactured by Nippon Synthetic Rubber Co., Ltd., trade name:" TR200 "-Block copolymer: Styrene-butadiene-styrene resin manufactured by Asahi Kasei Corporation
Product name “TUFPRENE 315” Tackifier: Arakawa Chemical Co., Ltd. product name “KE60
4) Process oil: a product of Shell Chemical Co., Ltd., trade name "Shellflex 371N" Table 1 shows the composition of the test adhesive as a ratio of other components to the base polymer.

[0072]

[Table 1]

1-3 Constituent support SUS plate

1-4 Curable clear coating agent Kansai Paint Co., Ltd. product name "CG Clear" Daicel UCB Co., Ltd. product name "KRM7039"

2. Example 1 Preparation of heat-bonded polyester film and coated body Example 1 One side of PET was preliminarily coated with an adhesive A-1 compound in ethyl acetate /
Solution dissolved in toluene 1/1 mixed solvent (solid content 40N
v percent) with a gravure roll coater to form a hot-melt adhesive layer having a dry thickness of 5 μm,
A heat-bondable polyester film was produced. Then, the film was placed on a SUS plate using a hot plate sealing machine,
Pressing was performed at a temperature of 10 ° C. for 10 seconds under a pressure of 10 kg / cm ² to prepare a polyester film-coated product.

Example 2 A heat-bondable film and a coated product were produced in the same manner as in Example 1, except that PBT was used instead of PET.

Example 3 PBT was used instead of PET, and ABT was used instead of A-1.
A heat-bondable film and a coated body were prepared in the same manner as in Example 1 except that the blend of -2 was used.

Example 4 PBT was substituted for PET and A-1 was substituted for ABT.
A heat-bondable film and a coated body were produced in the same manner as in Example 1 except that three blends were used.

Example 5 A heat-bondable film and a coated body were produced in the same manner as in Example 1 except that the composition A-3 was used instead of the composition A-1.

Example 6 CG clear was applied to the film surface of the polyester film coated and processed product prepared in Example 5 with a gravure roll coater so as to have a dry thickness of 2 μm, and was cured.

Example 7 KRM was applied to the film surface of the polyester-coated body produced in Example 5 with a gravure roll coater so as to have a dry thickness of 2 μm, and was cured.

Comparative Example 1 A control sample was prepared in the same manner as in Example 1 except that the compound A-1 was replaced with the compound A-4.

Comparative Example 2 A control sample was prepared in the same manner as in Example 2 except that the composition A-1 was replaced with the composition A-4.

Comparative Example 3 A control sample was prepared in the same manner as in Example 2 except that the composition A-1 was replaced with the composition A-5.

Comparative Example 4 A commercially available PVC steel sheet was used as Comparative Example 4.

3. Evaluation results of the polyester film-coated body The performance of each coated body sample was evaluated as described above, and the results are shown in Table 2 together with the configuration of the main part of each example.

[0087]

[Table 2] * 1) Adhesive coated surface. * 2) The surface of the SUS plate has a hairline finish. * 3) The adhesive surface of the film and the opposite surface are pressed with a simple tabletop press under the conditions of normal temperature, 10 seconds, and 100 g / cm ² . * 4) Using magic oil ink of "Magic Ink Large" manufactured by Teranishi Kagaku, apply magic to the surface of the coated workpiece 2
After 4 hours, dry with a Kimwipe and confirm the removability. A: All can be removed. ○: Some remain. ×: Remarkably remains.

When the results of the samples of Example 2 and Comparative Examples 1 to 3 are compared, the adhesion to the SUS plate has an order of magnitude difference, and the characteristics of the epoxidized block copolymer as the adhesive base polymer are clearly shown. It is shown. When an adhesive is applied to PET, the PET is peeled off from the adhesive, and P
When applied to the BT, it has peeled off between the adhesive and the SUS plate. When a tackifier is added, tackiness tends to occur and the film becomes difficult to handle. When the adhesive having the composition of A-3 is used, there is a tendency to cause cohesive failure in the adhesion to the SUS plate, and the handling of the film is easy because no tackifier is added. Furthermore, it can be seen that Examples-5 and 6 are particularly effective since the surface contamination prevention is further improved by applying the curable clear coat.

[0089]

As described above, the heat-bondable polyester film and the polyester film-coated product of the present invention are excellent in the adhesiveness to a rigid support, particularly to a metal plate.
In addition, by providing a hardening type clear coat on those surfaces, surface characteristics, particularly pollution prevention, can be further improved, so that interior and exterior building materials, furniture, kitchen utensils,
A wide variety of uses such as various housing materials and members or mark sheets are expected.

Claims (11)

[Claims] 1. A heat-bondable polyester film comprising a polyester film and a hot-melt adhesive layer having a base polymer of an epoxidized product of a vinyl aromatic compound-conjugated diene compound-based block copolymer on one surface. 2. A hot-melt adhesive layer comprising, on one side of a polyester film, a hot-melt adhesive layer mainly composed of an epoxidized vinyl aromatic compound-conjugated diene compound block copolymer, a tackifier, and process oil. Polyester film. 3. A hot-melt adhesive layer comprising 500 parts by weight or less (excluding 0 parts by weight) of a tackifier and 100 parts by weight of a process oil based on 100 parts by weight of a base polymer.
The heat-bondable polyester film according to claim 1, wherein the heat-bondable polyester film contains not more than 00 parts by weight (excluding 0 parts by weight). 4. The main component of the hot-melt adhesive layer is based on 100 parts by weight of the base polymer and 20 to 3 tackifiers.
3. The heat-bondable polyester film according to claim 1, wherein the heat-bondable polyester film contains 00 parts by weight and 20 to 300 parts by weight of a process oil. 5. The polyester film according to claim 1, wherein the polyester film is formed using a polyethylene terephthalate resin or a polybutylene terephthalate resin, or a polyethylene naphthalate resin or a polybutylene naphthalate resin as a main material. Heat-bondable polyester film. 6. A polyester film-coated body obtained by thermally bonding the heat-bondable polyester film according to claim 1 on a rigid support. 7. The coated body according to claim 6, wherein the support is a metal plate. 8. A curable clear coat is provided on the other surface of the heat-bondable film according to any one of claims 1 to 51 or 5 or on the surface of the coated body according to claim 6 or 7. A heat-bondable polyester film or a polyester film-coated article having enhanced surface contamination prevention properties. 9. The heat-bondable polyester film or polyester film-coated article according to claim 8, wherein the curable clear coat is mainly composed of an organopolysiloxane and / or an acrylic-modified polysiloxane. 10. The curable clear coat according to the following general formula (I) (In the formula, n represents an integer of 3 to 5, and R ¹ has 5 to 5 carbon atoms.
10 alcohol - R ² is Le residue is a hydrogen atom or a methyl group, R ³ organic diisocyanate - DOO a residue X compound 40-60 wt% and the following general represented by represents a urethane bond) Formula (II) (Wherein, R ¹ is an alcohol residue having 5 to 10 carbon atoms, R ² is a hydrogen atom or a methyl group, and n is 3 to 6
With respect to 100 parts by weight of a composition comprising 40 to 60% by weight of a compound represented by the following general formula: (Wherein n is an integer of 10 to 25, m1 and m2 represent 0 or an integer of 1 to 5, and R represents a methyl group or a hydrogen atom).
1 mol and a polyisoanate component represented by the following general formula (Wherein, R represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a substituted phenylene group) represented by the following formula: , Below, general formula (Wherein, R ¹ is an alcohol residue having at least one hydroxyl group and having 5 to 10 carbon atoms, R ² is a hydrogen atom or a methyl group, and n represents an integer of 3 to 5). 9. The heat according to claim 8, wherein the active energy ray-curable resin composition comprises 0.1 to 10 parts by weight of a polyfunctional urethane acrylate obtained by reacting the compound represented by the formula (I). Bondable polyester film or polyester film coated product. 11. A metal sheet having a thickness of 0.5 kg via an adhesive layer
The heat-bondable polyester film according to any one of claims 1 to 5, wherein the heat-bondable polyester film can be thermally bonded with an adhesive strength of / 25 mm width or more.