KR101709069B1 - Undercoating agent for plastic attachment inorganic thin layer, plastic attachment inorganic thin layer and decoration film for in-mold molding or insert molding - Google Patents

Abstract

(식(1)에서 R¹은 수소 또는 메틸기를, m은 0 또는 1을, X는 히드록시기를 구비하지 않는 알킬기, 히드록시기를 구비하지 않는 페닐기 또는 히드록시기를 구비하지 않는 벤질기를 나타낸다)

(식(2)에서 R²는 수소 또는 메틸기를, Y¹은 산소 또는 2급 아미노기(-NH-)를, n은 0 또는 1을, Y²는 히드록시기를 구비하는 알킬기, 히드록시기를 구비하는 페닐기 또는 히드록시기를 구비하는 벤질기를 나타낸다)(assignment)
An object of the present invention is to provide a novel undercoating agent which is excellent in adhesion to a metal thin film layer and the like and which does not cause whitening and large cracks on the metal surface even under a high temperature use environment.
(Solution)
Wherein the hydrophobic monomer (a1) represented by the following general formula (1) and the hydroxyl group-containing monomers (a2) represented by the following general formula (2) are reacted and the hydroxyl group concentration (mol / g) To 0.005 (A) and a polyisocyanate (B) having at least three isocyanate groups in the molecule is used as the undercoating agent.

(In the formula (1), R ¹ represents hydrogen or a methyl group, m represents 0 or 1, X represents an alkyl group not having a hydroxy group, a phenyl group not having a hydroxy group or a benzyl group having no hydroxy group)

(Wherein R ² represents hydrogen or a methyl group, Y ¹ represents oxygen or a secondary amino group (-NH-), n represents 0 or 1, Y ² represents an alkyl group having a hydroxy group, a phenyl group having a hydroxy group Or a benzyl group having a hydroxy group)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an undercoating film for an inorganic thin film-attached plastic, an inorganic thin film-attached plastic, and an edible film for an in-mold or insert molding.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to an undercoating agent used for adhering an inorganic thin film to a plastic substrate, particularly a plastic film.

A composite substrate obtained by applying (coating) an undercoating agent containing various polymers as main components to the surface of a plastic substrate and forming an inorganic thin film composed of aluminum or tin (hereinafter referred to as an inorganic thin film) (Hereinafter referred to as " plastic ") has been conventionally used in various fields such as a bottle, a cap, a gas barrier film and other packaging materials, Sheet (transparent conductive sheet), film condenser, and the like. In addition, an aluminum evaporated plastic film having a very thin aluminum layer, particularly about several tens of nanometers, among film-shaped inorganic thin film attached plastics is widely used as a member of a decorative film.

However, there is a problem in the inorganic thin film-attached plastic that a whitening portion (whitening portion) occurs on the inorganic thin film surface (inorganic thin film surface) at a high temperature regardless of its form. In addition, in the case of the plastic film with an inorganic thin film, not only a whitening portion is formed on the inorganic thin film surface at the time of molding under high temperature, but also cracks that can be judged by interference streaks or eyes on the inorganic thin film surface cracks may occur. These problems impair the technical function (gas barrier property, electromagnetic shielding property, etc.) and design property of the inorganic thin film-attached plastic film.

As a means for solving the whitening phenomenon, for example, Japanese Patent Application Laid-Open No. 60-40396 discloses a method of producing a polymeric polymer such as acryl copolymer, a polyisocyanate, An undercoating agent composed of a mixture of a small-scale polymer (fibrinous polymer) has been proposed. However, the above interference fringe is not specifically mentioned.

It is an object of the present invention to provide a novel undercoating agent which does not cause cracks or interference streaks which can be judged by visible white spot or eyes in the inorganic thin film even in close contact with both the inorganic thin film and the plastic and at a high temperature do.

As a result of intensive studies, the inventors of the present invention have found that when a predetermined monomer (a1) (hereinafter referred to as a component (a1)) and a monomer (a2) (hereinafter referred to as a component (a2) (hereinafter referred to as component (A)) having at least three isocyanate groups in the molecule and a polyisocyanate (B) (hereinafter referred to as component (B)) having at least three isocyanate groups in the molecule, By weight of the undercoating agent.

According to the undercoating agent of the present invention, a flat inorganic thin film can be formed on the surface of the plastic, and the adhesion between the inorganic thin film and the plastic becomes good. When a metal such as aluminum is used as the inorganic species, a thin film excellent in gloss can be obtained. Further, since the undercoat layer has good adhesion with the inorganic thin film layer, the inorganic thin film is difficult to fall off from the plastic substrate.

Among the obtained inorganic thin film-attached plastics, the film-shaped plastic is less susceptible to cracks, interference streaks, and whitening sites that can be visually judged on the inorganic thin film even when processed in a high temperature environment. The reason why interference fringes do not occur is not clear. However, as shown in Fig. 3, it is considered that cracks are generated in the inorganic thin film, but it is very fine and visible light does not interfere.

The inorganic thin film-adhered plastic film can be used as a packaging material such as a gas barrier film or a transparent conductive sheet, a film capacitor, a label for display (particularly a label for display), an edible film for use in insert molding (also referred to as a transfer foil) (Also referred to as a transfer foil) for in-mold molding, in which the molding process is performed under the condition that the mold is in contact with the mold.

1 is a microscopic photograph (400 times) of a vapor deposition surface in the aluminum-deposited PET film according to Example 8, and it is found that it is very smooth.
2 is a micrograph (1000 times) of the deposition surface of the aluminum-deposited PET film according to Comparative Example 5, showing a fine pattern over the entire surface. As a result of the irregular reflection of the visible light due to this pattern, it is considered that a whitening portion occurred on the vapor deposition surface.
3 is a microscopic photograph (3000 times) of the vapor deposition surface in the aluminum-deposited PET film according to Example 8. Fig.
4 is a microscopic photograph (3000 times) of the vapor deposition surface in the aluminum-deposited PET film of Comparative Example 1. Fig.
5 is a microscope photograph (3000 times) of the deposition surface of the aluminum-deposited PET film according to Comparative Example 5. Fig.

As the (a1) component represented by the general formula _{(1): CH 2 = C} (R 1) - a - [(C = O) -O- ] m R 1 is hydrogen or a methyl group in -X (formula (1), m Represents 0 or 1, X represents an alkyl group having no hydroxy group, a phenyl group having no hydroxy group or a benzyl group having no hydroxy group). The alkyl group may be any of straight chain, cyclic and branched. The phenyl group and benzyl group may have a substituent other than a hydroxy group.

Specific examples of the component (a1) include (metha) acrylic acid methyl, (meta) acrylic acid n-butyl, meta (meth) acrylate, acrylic acid isobutyl, (meta) acrylic acid octyl, (meta) acrylic acid 2-ethylhexyl, (meta) acrylic acid hexadecyl (Meta) acrylic acid octadecyl, (meta) acrylic acid docosyl, (meta) acrylic acid cyclopentyl, (meth) acrylic acid octadecyl, (Meta) acrylic acid cyclohexyl (metha) acrylic acid cyclohexane, (meta) acrylic acid cyclofentanyl, (meta) acrylic acid isobornyl, (meth) acrylic acid cyclohexyl metha acrylic acid phenyl, (meta) acrylic acid benzyl, (meta) acrylic acid 4-met (meta) acrylic acid alkylestheres such as methyl (meth) acrylate and ethyl (meth) acrylate; 2,4-trimethyl-1-pentene, 3-methyl-1-butene, 1-hexene, , Α-olefins (αolefins) such as vinylcyclohexane; And styrenes such as styrene,? -Methylstyrene, t-butylstyrene and the like. Of these, the (meth) acrylic acid alkyl esters, particularly those having an alkyl group of about 1 to 8 carbon atoms, are preferable because they are easy to polymerize with the components (a2) and (a3) desirable.

(2): CH ₂ ═C (R ² ) - [- (C═O) -Y ¹ -] _n -Y ² (In the formula (2), R ² represents hydrogen or a methyl group , Y ¹ represents oxygen or a secondary amino group (-NH-), n represents 0 or 1, Y ² represents a benzyl group having an alkyl group having a hydroxy group, a phenyl group having a hydroxy group or a hydroxy group) Use a flow. The alkyl group may be linear, cyclic or branched, and the phenyl group and the benzyl group may have a substituent.

Examples of the component (a2) include (meta) acrylic acid hydroxymethyl, (meta) acrylic acid hydroxyethyl, (meta) acrylic acid hydroxyethyl ) acrylic acid hydroxypropyl, (meta) acrylic acid 2-hydroxybutyl, (meta) acrylic acid 4-hydroxybutyl, (meth) acrylic acid hydroxy- (Meta) acrylic acid hydroxycyclohexyl, (meth) acrylic acid 4- (hydroxymethyl) cyclohexylmethyl, (metha) acrylic acid 4- (hydroxymethyl) cyclohexylmethyl, 2- hydroxypropionic acid 4- (hydroxymethyl) (Hydroxymethyl) cyclohexylmethyl, (meta) acrylic acid hydroxyphenyl, N- (2-hydroxyethyl) acrylamide (N- (2- hydroxyethyl acrylamide and N- (1-methyl-2-hydroxyethyl) acrylamide. Hydroxy (meth) acrylates, meta allyl alcohol, 4-pentene-1-ol, 1-methyl Unsaturated alcohols (unsaturated alcohols) such as 1-methyl-3-butene-1-ol and 5-hexene- . Among the components (a2), the hydroxy (meth) acrylates preferably have the carbon number of the hydroxyalkyl group (hydroxyalkyl group) is preferably in the range of, for example, 4 or less, especially 1 to 3 or less.

(3): CH ₂ ═C (R ³ ) - (CH ₂ ) _p --COOH (wherein R ³ represents a hydrogen or a methyl group and p represents a hydrogen atom or a methyl group) together with the component (a1) (Hereinafter referred to as a component (a3)) represented by the following formula (1), which is represented by an integer of 0 to 3, is used as the monomer (a3) crack resistance) is improved. This is presumably because the carboxyl group derived from the component (a3) functions as a catalyst for promoting the urethane formation reaction (uretaneization reaction) of the component (A) and the component (B) It is thought that this is due to the amidation reaction. Specific examples of the component (a3) include (metha acrylic acid), 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid Acid), and the like, but (metha) acrylic acid (metha) acrylic acid is preferable from the standpoint of availability and the like.

The component (A) can be prepared by various known methods. Specifically, for example, the component (a1), the component (a2) and, if necessary, the component (a3) are mixed with a radical polymerization initiator usually in the absence of a solvent or in an appropriate organic solvent, (Copolymerization reaction) at about 80 to 180 DEG C for about 1 to 10 hours.

The molar percentage of the components (a1) to (a3) is not particularly limited, but usually ranges from about 40 to 97 mol%, from 3 to 60 mol%, from 0 to 40 mol%, preferably from 45 to 80 mol% 15 to 55 mol% and 2 to 5 mol%.

Examples of the organic solvent include lower ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, aromatic hydrocarbons such as ethyl alcohol, alcohol such as ethyl alcohol and propyl alcohol, ether esters such as propyleneglycol mono methylether acetone and ethyl cellosolve acetate, ethers such as acetic acid (solid content weight) of the solution containing the component (A) is in the range of about 10 to 50% by weight, and the amount of the component to be.

Examples of the radical polymerization initiator include hydrogen peroxide (hydrogen peroxide), ammonium persulfate, potassium persulfate, t-butylperoxybenzoate, Dicumyl peroxide, lauryl peroxide, 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyrate), and the amount thereof to be used is usually about 0.1 to 2% by weight based on the total weight of the components (a1) to (a3).

The component (A) thus obtained has a hydroxyl group concentration (mol / g) of 0.001 to 0.005, preferably 0.0013 to 0.0037. The term "hydroxyl group concentration" refers to a calculated value representing the number of moles of the hydroxy group in 1 g of the component (A) (in terms of solid content). When it is less than 0.001, the whitening resistance and crack resistance tend to decrease, , There is a tendency that the production of the component (A) becomes difficult or the compatibility of the component (A) and the component (B) becomes insufficient.

When the component (a3) is used, the hydroxyl group concentration of the component (A) is the same and the concentration of the carboxyl group (mol / g) is usually about 0.0001 to 0.0035, preferably 0.0001 to 0.0006. The term " carboxyl group concentration " is a calculated value indicating the number of moles of carboxyl groups in 1 g of the component (A) (in terms of solid content), and the carboxyl group concentration is in this range, .

Further, other physical properties of the component (A) are not particularly limited, but the glass transition temperature is usually about 0 to 100 占 폚, particularly 15 to 80 占 폚 in terms of whitening resistance and crack resistance.

Further, the weight average molecular weight (weight average molecular weight) is usually about 3000 to 100000, particularly 10000 to 80000, and more preferably 40,000 to 70,000 in terms of whitening resistance and crack resistance.

As the polyisocyanate (B), any compound having at least three isocyanate groups (isocyanate groups) in the molecule can be used without particular limitation. The isocyanate group concentration (mol / g) of the component (B) is not limited, but is usually about 0.001 to 0.01, preferably 0.003 to 0.006. The term "isocyanate group concentration" refers to a calculated value representing the number of moles of isocyanate groups in 1 g of the component (B) (in terms of solid content), and the use of the component (B) .

Specific examples of the component (B) include diisocyanateurate (B-1) (hereinafter referred to as component (B-1)) represented by the following general formula (4)

(Formula 1)

(In the formula (4), R ⁴ represents any one of an aromatic diisocyanate residue, an aliphatic diisocyanate residue and a cyclic diisocyanate residue),

A diisocyanate adduct body (B-2) (hereinafter referred to as a (B-2) component) represented by the following general formula (5)

(2)

R ⁵ is -O-CH ₂ alkyl group having a carbon number of 1 to 3 or ^{OCN-R 6 -HN-C (} = O) in the (formula (5) - represents a functional group shown by R ⁶ is also an aromatic diisocyanate residue, An aliphatic diisocyanate residue, and a cyclic diisocyanate residue)

And a modified polyisocyanate (B-3) which is a reaction product of the component (B-1) and / or the component (B-2) with a compound having two active hydrogens capable of reacting with an isocyanate group in the molecule Hereinafter referred to as component (B-3)). Among them, the component (B-1) and / or the component (B-3) are preferred from the viewpoint of whitening resistance and crack resistance. Further, it is preferable that either component has an aromatic diisocyanate residue (residual group of aromatic diisocyanate). In consideration of the pot life of the undercoating agent, either component may block the isocyanate group with various protecting groups (protecting groups).

The term "diisocyanate residue" in each formula means the remaining groups in the diisocyanate compound (diisocyanate compound) constituting the component (B-1) or (B-2) except for the isocyanate group. Examples of the diisocyanate compound include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethanediisocyanate and xylylenediisocyanate; aromatic diisocyanates such as xylylenediisocyanate; Aliphatic diisocyanates such as hexamethylenediisocyanate, trimethylhexamethylenediisocyanate and lysinedisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylenediisocyanate and lysinedisocyanate; Examples thereof include dicyclohexylmethane diisocyanate, isoholondiisocyanate, 1,4-cyclohexanediisocyanate, hydrogenated xylenediisocyanate, hydrogenated tolylene diisocyanate (Hydrogenated tolyenediisocyanate), and other cyclic diisocyanates.

(B-1) and / or (B-2) constituting the component (B-3) preferably have an aromatic diisocyanate residue in terms of whitening resistance and crack resistance.

Specific examples of the compound having two active hydrogen atoms capable of reacting with an isocyanate group in the molecule include diol compounds having about 2 to 20 carbon atoms (preferably 4 to 8 carbon atoms), diamine compounds having about 2 to 20 carbon atoms, and water Water). Examples of the diol compound include ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, ), Neopentylglycol, 1,6-hexanediol, octanediol, dipropyleneglycol, and the like. However, it is also possible to use a copolymer having an excellent adhesion property, processability and heat resistance Particularly preferably 4 to 10 carbon atoms. Examples of the diamine compound include ethylene diamine, diethylene triamine, triethylene tetramine, isoholon diamine, and the like. The diol compound, diamine compound and water can be used in an amount such that the concentration of the isocyanate group in the obtained component (B-3) falls within the above range. The component (B-3) can be produced by various known methods, and if necessary, an organic solvent that does not react with an isocyanate group such as a lower ketone or an ether ester can be used.

The components (B-1) to (B-3) may all be used as a mixture. For example, when referring to the component (B-1), the diisocyanate nylate having an aromatic diisocyanate residue and the diisocyanate nylate having an aliphatic diisocyanate residue are usually used at a ratio of 9/1 to 1/9 Can be used as the component (B-1).

Examples of the polyisocyanate compound (polyisocyanate compound) other than the components (B-1) to (B-3) include lysine triisocyanate or hexafunctional polyisocyanate (product name: Dyuranate MHG- (Product of Asahi Kasei Chemical Co., Ltd., Japan) can be used in combination.

The undercoating agent of the present invention can be prepared by mixing the component (A) and the component (B) by various known methods. The ratio of the isocyanate groups (mol / g) of the component (B) to the grams (in terms of solid content) of the component X (B)] / [ (In terms of solid content) of the hydroxyl group concentration (mol / g) X (A) component of the component (A) is usually about 0.1 to 10, preferably 0.5 to 2.

The undercoating agent of the present invention is preferably used as a solution of the above-mentioned organic solvent, and its solid weight is usually about 5 to 50% by weight. In addition, the undercoating agent of the present invention may contain other additives such as an urethane forming catalyst (tin, tertiary amine, etc.), a leveling agent, an antioxidant and an ultraviolet absorber The reaction solvent (reaction solvent) may be added as an additive or a diluting solvent.

As the inorganic thin film-attached plastic of the present invention, a plastic structure with an inorganic thin film, a plastic film with an inorganic thin film, and the like may be cited according to the shape of the substrate. The shape of the plastic substrate constituting the structure is not particularly limited and may be, for example, a spherical shape, a columnar shape, a rectangular parallelepiped shape, a plate shape, There may be irregularities or curved surfaces. The inorganic thin film plastic film includes a plastic film, a layer made of the undercoating material of the present invention, and a layer made of an inorganic thin film. Examples of the plastic film include a polyester film, a polyvinyl chloride film, a polyamide film, a polyimide film, a polycarbonate film, a polyethylene film (polyethylene film) film, a polypropylene film, and the like. Examples of the inorganic thin film species (inorganic thin film species) include metals such as aluminum, gold, silver, palladium and tin, and metal oxides such as aluminum oxide, tin oxide, indium tin oxide, titanium oxide, .

The method for producing the inorganic thin film-attached plastic is not particularly limited. Specifically, for example, the coating agent of the present invention is applied to a plastic film substrate by various known methods and heat-treated at about 80 to 185 DEG C for about 10 seconds to 5 minutes to cure the undercoat layer, And further depositing the metal species by a known thin film formation method (thin film formation method). Examples of the application method include a spray, a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater, a dot coater, coater) and the like. The amount of application is not particularly limited, but is usually about 0.01 to 10 g / m ² as dry solid content. Examples of the means for forming the inorganic thin film include various physical methods (vacuum thermal evaporation, sputtering, etc.) and chemical methods (chemical vapor phase reaction, etc.). The thickness of the inorganic thin film is usually about 5 to 800 nm. In addition, it is preferable that an aluminum layer having a thickness of about 5 to 50 nm is included in the inorganic thin film-attached plastic film, and that the base material is a polyester film, especially a decorative film (transfer film) for in-mold molding or insert molding As shown in FIG.

The inorganic thin film-attached plastic of the present invention may have another functional layer (functional layer) depending on its use. For example, when the plastic film with an inorganic thin film of the present invention is used for an in-mold type transfer foil, a releasing layer, a hard coating layer, a hard coating layer, and a hard coating layer are interposed between the plastic film base layer and the undercoat layer. An anchor layer for a coating layer (anchor layer for a hard coating layer), a pattern ink layer and the like can be formed. An adhesive layer (adhesive layer) may be formed on the inorganic thin film layer.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto. Here, " parts " in the examples indicate weight standards. The glass transition temperature is a value measured using a commercially available measuring instrument (product name: " 8230B ", product of Rigaku Corporation, Japan). The weight average molecular weight (weight average molecular weight) was measured using a commercially available gel permeation chromatography apparatus (product name: HLC-8220GPC, manufactured by TOSOH CORPORATION) Value. The microscope photographs shown in Figs. 1 to 5 were taken using a commercially available confocal laser microscope (product name: VK-9500, manufactured by KEYENCE, Japan) .

(Production Example 1)

A reaction vessel equipped with a stirrer (stirrer), a thermometer, a reflux condenser (reflux condenser), a dropping funnel and a nitrogen inlet tube was charged with 36 parts of methyl methacrylate ( And about 111.6 parts (about 0.78 mol) of butyl methacrylate (about 82.1 mol% in the total amount of the components (a1) and (a2)) and 32.4 parts of 2-hydroxyethyl methacrylate ) (about 17.9 mol% in the total amount of the component (a1) and the component (a2)) and 270 parts of methyl ethyl ketone were charged, and the reaction system was set at 80 占 폚. Subsequently, 0.9 part of azobisisobutyronitrile was added, and the mixture was maintained at 80 DEG C for 5 hours. Subsequently, 1.8 parts of azobisisobutyronitrile was added, and the reaction system was further maintained at the same temperature for 3 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the desired copolymer (A-1) (hereinafter referred to as component (A-1)). Table 1 shows the raw material species, the hydroxyl group concentration, the carboxyl group concentration, the glass transition temperature and the weight average molecular weight of the component (A-1).

(Production Examples 2 to 25, Comparative Production Examples 1 to 3)

(A-2) to (A-25) and Comparative Copolymer ((A-2)) were prepared in the same manner as in Production Example 1, except that the type and the amount (mol%) of the monomers used were changed as shown in Table 1. A) and b) were prepared. The hydroxyl group concentration, the carboxyl group concentration, the glass transition temperature and the weight average molecular weight are shown in Table 1. Also, the copolymer (C) was not provided for further evaluation because the solution was cloudy.

The meanings of the symbols in Tables 1 and 2 are as follows.

MMA: methyl methacrylate

BMA: n-butyl methacrylate

nBA: n-butyl acrylate

St: Styrene

2HEMA: 2-hydroxyethyl methacrylate

2HEA: 2-hydroxyethyl acrylate

4HBA: 4-hydroxybutyl acrylate

CHDMMA: 2-Hydroxypropionic acid 4- (hydroxymethyl) cyclohexylmethyl

HEAA: N- (2-hydroxyethyl) acrylamide

CHA: cyclohexyl acrylate

IBOA: isobornyl acrylate

DCPA: dicyclopentanil acrylate

MAA: methacrylic acid

OH Concentration: Hydroxy Group Concentration

COOH concentration: carboxyl group concentration

Tg: glass transition temperature

Mw: weight average molecular weight

(Preparation Example 26)

445.5 parts of a nylate of tolylene diisocyanate (trade name: "CORONATE 2030", isocyanate group concentration of 3.8 × 10 ^-3 mol / g) and 1,6-hexanediol were added to the same reaction vessel as in Production Example 1 And 55.6 parts of methyl ethyl ketone, and the urethanization reaction was carried out at 60 占 폚 for 3 hours. Thereafter, the mixture was cooled to room temperature to obtain a modified tolylene diisocyanate nylon (hereinafter referred to as "modified TDI-1", isocyanate group concentration of 1.5 × 10 ^-3 mol / g).

(Preparation Example 27)

445.5 parts of the above Coronate 2030, 0.75 part of water, 25.2 parts of methyl ethyl ketone and 25.2 parts of propylene glycol monomethyl ether acetate were put into the same reaction vessel as that of Production Example 1 and the urethanization reaction was carried out at 60 占 폚 for 3 hours . Thereafter, the mixture was cooled to room temperature to obtain a modified tolylene diisocyanate nylon (hereinafter referred to as "modified TDI-2", isocyanate group concentration of 1.5 × 10 ^-3 mol / g).

(Examples 1 to 25)

An undercoating agent was prepared according to the components (A), (B) and mixing ratio shown in Table 3. At this time, methyl ethyl ketone was used as a diluting solvent to prepare a solid content concentration of 15% by weight (hereinafter the same).

(Examples 26 to 38)

An undercoating agent was prepared according to the components (A), (B) and mixing ratio shown in Table 4.

(Examples 39 to 59)

An undercoating agent was prepared according to the components (A), (B) and mixing ratio shown in Table 5.

(Examples 60 and 61)

An undercoating agent was prepared according to the components (A), (B) and mixing ratio shown in Table 6.

(Comparative Examples 1 to 10)

An undercoating agent was prepared according to the components (A), (B) and mixing ratio shown in Table 7.

(Comparative Examples 11 to 32)

An undercoating agent was prepared according to the components (A), (B) and mixing ratio shown in Table 8.

≪ Preparation of Test Film >

The undercoating agent according to Example 1 was coated on a commercially available polyethylene terephthalate film (trade name: E5100, TOYOBO, Japan, thickness: 16 μm) to a dry film thickness of 1 μm by a bar coater Respectively. Subsequently, the coating film thus obtained was cured (150 DEG C, 60 seconds) by a circulating air drier. Subsequently, the coated film was coated with an aluminum evaporated film having a thickness of 50 nm as a vapor deposition apparatus (commercially available from NISHIYAMA SEISAKUSHO., LTD., Japan) using a commercially available vapor deposition apparatus (product name: NS-1875- . This was used as the test film of Example 1. Test films were prepared in the same manner for the undercoating agents of other examples and comparative examples.

(Appearance after curing treatment)

The aluminum deposition side of each test film was visually observed, and there was no fogging or whitening on the glossy surface (indicated by o in each table).

(Adhesion)

On each of the test films, an adhesive tape (product name: "Cellotape", product of NICHIBAN, Japan) was attached to the aluminum evaporated surface and the aluminum surface was peeled off in the vertical direction In Fig.

(White Mars)

The whitening conditions of the test films of each of the examples and comparative examples were visually evaluated based on the following criteria.

○ (5 points): A state in which whitening does not occur on the aluminum surface

○ △ (4 points): A state in which whitening occurs partially on the aluminum surface

? (3 points): a state in which whitening occurs slightly on the entire aluminum surface

ΔX to X (2 points to 1 point): A state in which whitening or interference stripes are strongly generated on the entire aluminum surface

(4 points)> Δ (3 points)> ΔX (2 points)> X (2 points) where X, Y, (One point) is effective in ranking. Hereinafter, it is the same in this specification)

(Crack resistance)

The undercoating agent of Example 1 was applied to a commercially available acrylic panel (product name "Como Glass", product of KURARAY, Japan, 5 cm × 5 cm × 1 mm) by a bar coater so that the dry film thickness became 1 μm , And cured with a circulating air dryer (at 150 DEG C for 60 seconds) to prepare a test panel for crack resistance test. Test panels were also prepared in the same manner for the undercoating agents of other examples and comparative examples.

On the other hand, an aluminum plate (15 cm X 5 cm X 1 mm) was folded at 60 degrees from the center of the plate, and a bending mechanism for the test panel was manufactured. Subsequently, the apparatus was heated in a circulating air dryer (250 ° C), and the test panel of Example 1 was pressed on the bent side of the apparatus from the acrylic panel side for about 3 seconds to fold it at about 80 °. Thereafter, the state of the aluminum deposition layer at the bending portion was visually evaluated based on the following criteria. The test panels of the other examples and comparative examples were also visually evaluated in the same manner.

○ (5 points): There is no cracking or peeling at the aluminum deposition site, and no fogging or interference stripes

○ △ (4 points): There is no cracking or peeling in the aluminum deposition area, and there is little cloudiness and no interference stripes

△ (3 points): There is no break or peeling in the aluminum deposition area, and there is a slight clouding or interference stripes

△ X (2 points): There is a thin crack or peeling at the aluminum deposition site, and there is a strong cloudiness or interference stripes

X (1 point): There is a large crack or peeling in the aluminum deposition area, and there is a strong cloudiness or interference stripes

Further, in this test, by using a thick acrylic panel, the undercoating surface (layer) is excessively stretched in the bending direction of the panel at a high temperature, resulting in a situation where cracks are more likely to occur in the aluminum vapor deposition layer. These harsh tests are predicated on the actual machine of the in-mold injection molding.

Example 62

An undercoating agent was prepared from the components (A), (B) and mixing ratio shown in Table 9. Subsequently, the undercoating agent was applied in the same manner as above to prepare a film. Then, a tin-plated film having a thickness of 50 nm was obtained by the above-described vapor deposition apparatus. Subsequently, the film appearance, whitening resistance and crack resistance after the curing treatment were evaluated in the same manner as above. The results are shown in Table 9.

In Tables 3 to 9, the symbols in component (B) have the following meanings.

C-2030: abbreviation of "CORONATE 2030", NIPPON POLYURETHANE INDUSTRY CO., LTD., Product of Japan, nylate of tolylene diisocyanate (isocyanate group concentration 3.8 X 10 < ^-3 > mol / g)

V-T1890: an abbreviation of "VESTANT T1890E", a product of Degussa of Japan, a nylate of isophthalone diisocyanate (isocyanate group concentration of 4.0 × 10 ^-3 mol / g)

(Isocyanate group concentration: 5.0 X 10 <" ³ > mol / g) of hexamethylene diisocyanate, C-HX: abbreviation of Coronate HX, product of Nippon Paint Co.,

D-103M2: an abbreviation of "Takenate D-103M2", a product of Mitsui Chemical Company, Japan, a 3: 1 adduct of tolylene diisocyanate and trimethylol propane (isocyanate group concentration of 3.8 × 10 ^-3 mol / g)

MH-G80B: an abbreviation of "Dyuranate MHG-80B", a product of Asahi Kasei Chemical Co., Ltd. of Japan, hexamethylene diisocyanate-based hexafunctional polyisocyanate (isocyanate group concentration of 4.4 × 10 ^-3 mol /

Modified TDI-1: Modified tolylene diisocyanate nuruate of Production Example 26

Modified TDI-2: Modified tolylene diisocyanate nuruate of Production Example 27

IPDI: isophorone diisocyanate (isocyanate group concentration: 9 * 10 ^-3 mol / g)

Claims (12)

(A1) represented by the following general formula (1) and the monomers (a2) represented by the following general formula (2) are reacted and the hydroxyl group concentration (hydroxy group concentration) (mol / (B) having at least three isocyanate groups (isocyanate groups) in the molecule and a copolymer (A) having a number average molecular weight (g) of from 0.001 to 0.005 and a polyisocyanate Undercoating agent for attachment plastic (for inorganic thin film attachment plastic).

(In the formula (1), R ¹ represents hydrogen or a methyl group, m represents 0 or 1, X represents an alkyl group having no hydroxy group, a phenyl group having no hydroxy group ) Or a benzyl group (benzyl group) having no hydroxy group)

(2), R ² represents hydrogen or a methyl group, Y ¹ represents an oxygen atom or a secondary amino group (secondary amino group) (-NH-), n represents 0 or 1, Y ² represents a hydroxy group An alkyl group, a phenyl group having a hydroxy group or a benzyl group having a hydroxy group)
The method according to claim 1,
Wherein the component (A) is further reacted with the monomer (a3) represented by the following general formula (3).

(In the formula (3), R ³ represents hydrogen or a methyl group, and p represents an integer of 0 to 3)
3. The method of claim 2,
(Carboxyl group concentration) (mol / g) of the component (A) is 0.0001 to 0.0035.
4. The method according to any one of claims 1 to 3,
Wherein the isocyanate group concentration (isocyanate group concentration) (mol / g) of the polyisocyanate (B) is 0.001 to 0.01.
3. The method according to claim 1 or 2 ,
The polyisocyanate (B) is a diisocyanateurate (B-1) represented by the following general formula (4)
(Formula 1)

(In the formula (4), R ⁴ represents any one of an aromatic diisocyanate residue (residual group of aromatic diisocyanate), an aliphatic diisocyanate residue (residual group of aliphatic diisocyanate), and a cyclic diisocyanate residue ),
The diisocyanate adduct (B-2) represented by the following general formula (5)
(2)

R ⁵ in the (expression 5 is an alkyl group or ^{OCN-R 6 -HN-C (} = O) -O-CH 2 with a carbon number of 1 to 3 - represents a functional group (官能基indicated by) R ⁶ is also an aromatic A diisocyanate residue, an aliphatic diisocyanate residue, and a cyclic diisocyanate residue)
And
A modified polyisocyanate (B-2), which is a reaction product of the component (B-1) and / or the component (B-2) with a compound having two active hydrogens (active hydrogen) capable of reacting with an isocyanate group in the molecule, 3). ≪ / RTI >
3. The method according to claim 1 or 2 ,
(Mol / g) of the component (A) and the component (B) in a ratio of (isocyanate group concentration of the component (B) (g) (grams of the component (A)) (in terms of solid content) is 0.1 to 10.
4. The method according to any one of claims 1 to 3 ,
An undercoating agent characterized by being used as a solution of an organic solvent.
An inorganic thin film attachment plastic (inorganic thin film attachment plastic) comprising a layer (layer) made of the undercoating agent according to any one of claims 1 to 3 .
9. The method of claim 8,
Wherein the inorganic thin film layer (inorganic thin film layer) is an aluminum layer.
10. The method of claim 9,
Wherein the inorganic thin film-attached plastic is in the form of a film.
An edible film for in-mold molding (in-mold decorative film), characterized in that the inorganic thin film-attached plastic according to claim 10 is a member.
An edible decorative film for insert molding (insert film for insert molding) characterized by comprising the inorganic thin film-attached plastic according to claim 10.

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