KR101976550B1

KR101976550B1 - Primer composition and stacked material

Info

Publication number: KR101976550B1
Application number: KR1020177007504A
Authority: KR
Inventors: 데루 사카키바라; 고지 마에다; 신야 고마비키
Original assignee: 고오 가가쿠고교 가부시키가이샤
Priority date: 2014-09-16
Filing date: 2015-03-06
Publication date: 2019-05-09
Also published as: JPWO2016042683A1; JP6346669B2; CN106715612B; CN106715612A; WO2016042683A1; KR20170042777A

Abstract

The present invention provides a hydrophilic primer composition which is capable of imparting adhesiveness to a base material by being applied to a base material and having good handling properties. The primer composition according to the present invention contains a polyester resin having a polyvalent carboxylic acid residue and a glycol residue, and a modified polyolefin resin. The polyvalent carboxylic acid residue includes at least one of a polyvalent carboxylic acid residue having a trivalent or more valence and a polyvalent carboxylic acid residue having a metal sulfonate group. The value of the mass ratio of the polyester resin to the modified polyolefin resin is in the range of 8/2 to 2/8.

Description

[0001] PRIMER COMPOSITION AND STACKED MATERIAL [0002]

The present invention relates to a primer composition and a lamination member, and more particularly to a primer composition for forming a primer layer and a lamination member having a primer layer formed of the primer composition.

Various base materials such as films made of polyolefin resin such as polypropylene and polyethylene are coated with an ink for the purpose of printing or a metal deposition layer is formed for imparting gas barrier property . In the case where the substrate has low adhesiveness to a coating film, ink, metal or the like as in the case where the substrate does not have a polar group, the surface of the substrate may be subjected to corona discharge, plasma treatment, frame treatment, ultraviolet irradiation treatment, Processing may be performed.

However, such a surface treatment involves a problem involving a risk. Further, there is also a problem that the adhesiveness improved by the surface treatment tends to deteriorate with time.

Conventionally, in order to improve the adhesiveness of the substrate, a primer having excellent adhesiveness is applied to the substrate.

As such a primer, for example, there is a primer containing an organic solvent such as toluene as a main component. However, when the primer contains an organic solvent, problems such as deterioration of the working environment arise.

In addition, International Publication WO2010 / 038643 discloses a process for producing an unsaturated polyester resin which comprises a monomer having at least one unsaturated compound having a hydroxyl group and at least one unsaturated compound selected from the group consisting of unsaturated carboxylic acid esters, styrene, unsaturated carboxylic acids, unsaturated hydrocarbons, vinyl esters and vinyl halides A primer comprising a main component (A) made of a copolymer, a curing agent (B) composed of a compound having an isocyanate group, and a compound (C) having at least two carboxylic acid groups and at least one carboxylic acid group in one molecule .

However, the two-component curing type primer containing a crosslinking agent such as a polyfunctional isocyanate disclosed in Patent Document 1 has a problem that the handling property is poor since it must be used promptly after mixing the main component with a curing agent.

International Publication WO2010 / 038643

Disclosure of the Invention The present invention has been made to solve the above problems, and it is an object of the present invention to provide a hydrophilic primer composition capable of imparting adhesiveness to a substrate and having good handling properties, and a lamination member comprising a primer layer formed of the primer composition The purpose is to provide.

The primer composition according to the present invention comprises a polyester resin having at least one of a polyvalent carboxylic acid residue having a trivalent or higher polyvalent carboxylic acid residue and a polyvalent carboxylic acid residue having a metal sulfonate group,

A modified polyolefin resin,

The value of the mass ratio of the polyester resin to the modified polyolefin resin is in the range of 8/2 to 2/8.

The acid value of the polyester resin is preferably in the range of 2 to 100 mgKOH / g.

The percentage of the polyvalent carboxylic acid residue having the metal sulfonate group to the total polyvalent carboxylic acid residue in the polyester resin is preferably within a range of 1 to 60 mol%.

The modified polyolefin resin preferably contains an acid-modified polyolefin resin.

The acid-modified polyolefin resin preferably contains at least one of a maleic acid-modified polyolefin resin and a maleic anhydride-modified polyolefin resin.

The modified polyolefin resin is preferably not chlorinated.

In the lamination member according to the present invention,

A substrate,

And a primer layer on the substrate and made from the primer composition.

The lamination member may further comprise an outer layer made of metal or resin on the primer layer.

According to the present invention, it is possible to obtain a hydrophilic primer composition which can impart adhesiveness to a base material and has good handling properties.

Further, according to the present invention, it is possible to obtain a lamination member having a primer layer formed of a hydrophilic primer composition which can impart adhesiveness to a substrate and has good handling properties.

1 is a cross-sectional view showing a lamination member in an embodiment of the present invention.

The primer composition according to the present embodiment contains a polyester resin and a modified polyolefin resin.

The primer composition is used, for example, to obtain the lamination member 1 as shown in Fig. The laminate member 1 comprises a base material 2, a primer layer 3 on the base material 2 and made of a primer composition, and an outer layer 4 of metal or resin on the primer layer 3 Respectively.

The polyester resin has a polyvalent carboxylic acid residue and a glycol residue.

The polyester resin has at least one of a polyvalent carboxylic acid residue having a trivalent or more valence and a polyvalent carboxylic acid residue having a metal sulfonate group. That is, the polyvalent carboxylic acid residue in the polyester resin contains at least one of a polyvalent carboxylic acid residue having a trivalent or more valence and a polyvalent carboxylic acid residue having a metal sulfonate group. When the polyvalent carboxylic acid residue contains a trivalent or higher polyvalent carboxylic acid residue, unreacted carboxyl groups are likely to remain in the polyvalent carboxylic acid residue having three or more valences. Therefore, when the polyvalent carboxylic acid residue contains a polyvalent carboxylic acid residue having three or more valences, the polyester resin has a carboxyl group derived from the polyvalent carboxylic acid residue. When the polyvalent carboxylic acid residue contains a polyvalent carboxylic acid residue having a metal sulfonate group, the polyester resin has a metal sulfonate group derived from a polyvalent carboxylic acid residue having a metal sulfonate group. Therefore, the polyester resin has at least one of a carboxyl group and a metal sulfonate group having a polarity, and accordingly, the polyester resin has water solubility and also has a metal, a resin having a polar portion Adhesion is also given.

The acid value of the polyester resin is preferably in the range of 2 to 100 mgKOH / g. In this case, high water solubility is imparted to the polyester resin, and high adhesiveness to the base resin (2), metal, resin and the like is also imparted to the polyester resin. The acid value of the polyester resin is more preferably in the range of 5 to 100 mgKOH / g, more preferably in the range of 20 to 80 mgKOH / g, still more preferably in the range of 30 to 70 mgKOH / g, Particularly preferably in the range of 35 to 68 mgKOH / g. By appropriately changing the acid value of the polyester resin, the molar ratio of the polyvalent carboxylic acid residue to the glycol residue in the polyester resin, and the ratio of the polyvalent carboxylic acid residue to the total polyvalent carboxylic acid residue in the polyester resin, . That is, the acid value of the polyester resin is preferably from 2 to 100 mgKOH / g, more preferably from 2 to 100 mgKOH / g, more preferably from 3 to 100 mgKOH / g, Is adjusted to be in the range of 5 to 100 mg KOH / g, more preferably 20 to 80 mg KOH / g, still more preferably 30 to 70 mg KOH / g, particularly preferably 35 to 68 mg KOH / g do.

When the polyester resin has a polyvalent carboxylic acid residue having a metal sulfonate group, the percentage of the polyvalent carboxylic acid residue having a metal sulfonate group to the entire polyvalent carboxylic acid residue in the polyester resin is within a range of 1 to 60 mol% , More preferably in the range of 1 to 30 mol%, further preferably in the range of 1 to 20 mol%, and particularly preferably in the range of 2 to 18 mol%.

The weight average molecular weight of the polyester resin is preferably in the range of 3000 to 100000, more preferably in the range of 4000 to 80000, and particularly preferably in the range of 5000 to 60000. When the weight average molecular weight is too low, the tackiness of the primer layer 3 at room temperature tends to increase. When the weight average molecular weight is too high, the solubility or dispersibility of the polyester resin in a solvent tends to be lowered. The weight average molecular weight of the polyester resin is easily adjusted by appropriately setting the synthesis conditions of the polyester resin. The weight average molecular weight of the polyester resin is a value measured by gel permeation chromatography (in terms of polystyrene).

On the other hand, the modified polyolefin resin is a polyolefin resin modified to have a group having polarity. That is, the modified polyolefin resin has a skeleton of a polyolefin which is a non-polar region and a portion having a polarity introduced by the modification. Since the modified polyolefin resin has a non-polar polyolefin skeleton, the modified polyolefin resin has adhesion to a non-polar material. Further, since the modified polyolefin resin has a portion having polarity, the modified polyolefin resin has water-solubility.

The value of the mass ratio of the polyester resin to the modified polyolefin resin is in the range of 8/2 to 2/8. When the mass ratio of the polyester resin is within the above-mentioned range, a site having a suitable polarity is imparted to the primer composition, and the primer layer 3 formed with the primer composition is given good adhesion to metal, resin having polarity, and the like. If the mass ratio of the modified polyolefin resin is within the above-mentioned range, an appropriate non-polar region is imparted to the primer composition, and good adhesion to the non-polar material is imparted to the primer layer 3 formed of the primer composition. As a result, the primer layer 3 formed of the primer composition has excellent adhesion to metals, resins, and the like. The value of the mass ratio of the polyester resin to the modified polyolefin resin is particularly preferably in the range of 7/3 to 3/7. In this case, the primer layer 3 formed of the primer composition has particularly excellent adhesion to metals, resins and the like.

The polyester resin and the modified polyolefin resin will be described in more detail.

The polyester resin will be explained.

Examples of the polyvalent carboxylic acid residue having a trivalent or higher valence include residues such as a hemimellitic acid residue, a trimellitic acid residue, a trimesic acid residue, a melomaric acid residue, a pyromellitic acid residue, a benzenepentacarboxylic acid residue, a melitic acid residue, At least one group selected from the group consisting of 1,2,3-tricarboxylic acid residue, cyclopentane-1,2,3,4-tetracarboxylic acid residue, and ethanetetracarboxylic acid residue.

As the polyvalent carboxylic acid residue having a metal sulfonate group, a dicarboxylic acid residue having a metal sulfonate group can be exemplified. More specifically, the polyvalent carboxylic acid residue having a metal sulfonate group is, for example, a residue of a 5-sulfoisophthalic acid residue, a residue of a 2-sulfoisophthalic acid residue, a residue of a 4-sulfoisophthalic acid residue, And at least one group selected from the group consisting of 4-sulfonaphthalene-2,6-dicarboxylic acid residues.

The polyvalent carboxylic acid residue in the polyester resin may further contain a dicarboxylic acid residue such as an aromatic dicarboxylic acid residue or an aliphatic dicarboxylic acid residue in addition to a polyvalent carboxylic acid residue having a polyvalent carboxylic acid residue and a metal sulfonate group having three or more valences, You may. Examples of the aromatic dicarboxylic acid residue include terephthalic acid residue, isophthalic acid residue, phthalic acid residue, diphenic acid residue, naphthalic acid residue, 1,2-naphthalenedicarboxylic acid residue, 1,4-naphthalenedicarboxylic acid residue, , 5-naphthalene dicarboxylic acid residue, and 2,6-naphthalene dicarboxylic acid residue. The aliphatic dicarboxylic acid residue can be, for example, a straight chain, branched and alicyclic oxalic acid residue, malonic acid residue, succinic acid residue, maleic acid residue, itaconic acid residue, glutaric acid residue, adipic acid residue, An isomeric residue, a sebacic acid residue, a dodecanedioic acid residue, a 1,3-cyclopentanedicarboxylic acid residue, a 1,4-cyclohexanedicarboxylic acid residue, a 2,2-dimethylglutaric acid residue, A polyglycolic acid residue, a diglycolic acid residue, and an odiphopropionic acid residue. A terephthalic acid residue, an isophthalic acid residue and a 2,6-naphthalenedicarboxylic acid residue in the aromatic dicarboxylic acid residue, and a succinic acid residue, adipic acid residue, sebacic acid residue, dodecanedioic acid residue, The 4-cyclohexanedicarboxylic acid residue is preferable in view of easiness of reaction, adhesion of the obtained resin, weather resistance (weather resistance), durability (durability) and the like. Particularly, it is most preferable that the aromatic dicarboxylic acid residue and the 1,4-cyclohexanedicarboxylic acid residue are the main components of the polyvalent carboxylic acid residue.

The glycol residue may be, for example, a polyethylene glycol such as ethylene glycol residue, diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, pentaethylene glycol residue, hexaethylene glycol residue, heptaethylene glycol residue or octaethylene glycol residue Residue; A polypropylene glycol residue such as propylene glycol residue, dipropylene glycol residue, tripropylene glycol residue, and tetrapropylene glycol residue; 1,3-propanediol residue, 1,3-butanediol residue, 1,4-butanediol residue, 1,5-pentanediol residue, 1,6-hexanediol residue, 2,2- Ethyl-2-butyl-1,3-propanediol residue, 2-ethyl-2-isobutyl-1,3-propanediol residue, 2,2,4-trimethyl-1,6-hexanediol residue , 1,2-cyclohexane dimethanol residue, 1,3-cyclohexane dimethanol residue, 1,4-cyclohexane dimethanol residue, 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue, A 4,4'-dihydroxyphenol residue, a 4,4'-methylenediphenol residue, a 4,4'-isopropylidenediphenol residue, a 1,5-dihydroxynaphthalene residue, At least one group selected from the group consisting of a hydroxy naphthalene residue, a 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) residue, and a bisphenol S residue.

In particular, the glycol moiety may be an ethylene glycol moiety; Diethylene glycol residue; Butanediol residues such as 1,4-butanediol residues; A hexanediol residue such as a 1,6-hexanediol residue; 1,4-cyclohexanedimethanol residues; Neopentyl glycol residue; And at least one group selected from the group consisting of a bisphenol A residue. In this case, the synthesis of the polyester resin is easy, and the polyester resin has high durability.

The polyester resin is obtained, for example, by polymerizing a reactive raw material containing a compound having an ester-forming functional group. The ester-forming functional group means a functional group capable of reacting with a carboxyl group or a hydroxyl group to form an ester bond. The ester-forming functional group includes a carboxyl group, a hydroxyl group, an ester-forming inducing group of a carboxyl group, and an ester-forming inducing group of a hydroxyl group. The ester-forming inducible group of a carboxyl group is a group obtained by reacting a compound with a carboxyl group and capable of forming an ester bond by reacting with a hydroxyl group. Specific examples of the ester-forming inducible group of the carboxyl group include, for example, a group obtained by anhydride-forming a carboxyl group, a group obtained by esterifying a carboxyl group, a group obtained by acidifying a carboxyl group, and a group obtained by halogenating a carboxyl group. The ester-forming inducible group of the hydroxyl group is a group obtained by reacting a compound with a hydroxyl group and capable of forming an ester bond by reacting with a carboxyl group. Specific examples of the ester-forming inducing group of a hydroxyl group include groups obtained by acetylating a hydroxyl group. Particularly, it is preferable that the ester-forming functional group is a carboxyl group or a hydroxyl group because the reactivity at the time of production of the polyester resin becomes favorable.

The reactive raw material includes a polyvalent carboxylic acid component corresponding to the polyvalent carboxylic acid residue in the polyester resin and a glycol component corresponding to the glycol residue in the polyester resin. The polyvalent carboxylic acid component includes at least one compound selected from the group consisting of a polyvalent carboxylic acid and an ester-forming derivative of a polyvalent carboxylic acid. The ester-forming derivative of the polyvalent carboxylic acid is a compound in which a carboxyl group in the polyvalent carboxylic acid is substituted with an ester-forming induction group of a carboxyl group. The glycol component includes at least one compound selected from the group consisting of a glycol and an ester-forming derivative of a glycol. The ester-forming derivative of the glycol is a compound in which the hydroxyl group in the glycol is substituted with an ester-forming induction group of a hydroxyl group.

The molar ratio of the polyvalent carboxylic acid component to the glycol component contained in the reactive raw material is preferably in the range of 1: 1 to 2.5.

The polyester resin is synthesized from a reactive raw material by a known polyester production method. For example, a polyester resin is synthesized by a direct esterification reaction in which a polycarboxylic acid and glycol are reacted in one step reaction.

When the polyvalent carboxylic acid component contains an ester forming derivative of a polyvalent carboxylic acid and the glycol component contains glycol, a first stage reaction which is an ester exchange reaction between an ester forming derivative of a polyvalent carboxylic acid and a glycol, A polyester resin may be synthesized through a second-step reaction in which the reaction product by the step reaction is polycondensed. In the first step reaction, all of the reactive raw materials may be contained in the reaction system from the beginning, and a part of the reactive raw materials may be added to the reaction system during the ester polycondensation reaction. In the first step reaction, when all of the reactive raw materials are contained in the reaction system from the beginning, for example, the reaction system is gradually heated to 150 to 260 캜 under an atmospheric pressure condition in an inert gas atmosphere such as nitrogen gas, The ester exchange reaction proceeds by heating. The second-step reaction proceeds under a reduced pressure of, for example, 6.7 hPa (5 mmHg) or lower, within a temperature range of 160-280 캜.

In the first step reaction and the second step reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds and the like may be added as catalysts to the reaction system at any time.

The modified polyolefin resin will be described.

The modified polyolefin resin is a polyolefin resin modified to have a group having polarity as described above. The modified polyolefin resin may contain a resin obtained by modifying the polyolefin resin with at least one polarity-imparting agent selected from acid, chlorine and a radical polymerizable monomer. The modified polyolefin resin may also be modified with an ethylene? -Olefin copolymer. In particular, the modified polyolefin resin preferably contains at least one of an acid-modified polyolefin resin and a polyolefin resin modified with (meth) acrylamide which is a radical polymerizable monomer. It is preferable that the polarity-imparting agent does not contain chlorine. That is, it is preferable that the modified polyolefin resin is not chlorinated.

The polyolefin resin is, for example, a polymer of a monomer containing an alkene having 2 to 8 carbon atoms. The alkene having 2 to 8 carbon atoms is, for example, at least one kind selected from the group consisting of ethylene, propylene, isobutylene, 2-butene, 1-butene, &Lt; / RTI > compounds.

The acid-modified polyolefin resin is, for example, modified with an unsaturated carboxylic acid. The unsaturated carboxylic acids include at least one of an unsaturated carboxylic acid and a derivative thereof. Derivatives of unsaturated carboxylic acids include unsaturated carboxylic anhydrides and esters of unsaturated carboxylic acids.

Examples of the unsaturated carboxylic acids include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, half ester of unsaturated dicarboxylic acid, Amide, and the like. It is particularly preferable that the unsaturated carboxylic acids contain at least one of maleic acid and maleic anhydride. That is, it is preferable that the acid-modified polyolefin resin contains at least one of a maleic acid-modified polyolefin resin and a maleic anhydride-modified polyolefin resin.

The acid-modified polyolefin resin is obtained, for example, by copolymerizing an unsaturated carboxylic acid and an alkene. The unsaturated carboxylic acids and alkenes may be randomly copolymerized, block copolymerized, or graft copolymerized.

(Meth) acrylamide includes at least one of acrylamide and methacrylamide. That is, the (meth) acrylamide-modified polyolefin resin is modified to at least one of acrylamide and methacrylamide.

The (meth) acrylamide-modified polyolefin resin is obtained by, for example, copolymerizing (meth) acrylamide with an alkene. The (meth) acrylamide and the alkene may be random copolymerized, block copolymerized or graft copolymerized.

Specific examples of the modified polyolefin resin include Out Lauren (trade name) manufactured by Japan Paper Co., Ltd., APTOLOK (trade name) manufactured by Mitsubishi Chemical Corporation, GENPOLY (trade name) manufactured by LOTTE CHEMICAL CORPORATION, Sumitof manufactured by Chemtex Co., Ltd., SUPERCRON manufactured by Japan Paper Co., Ltd., Wintec manufactured by Nippon Polypropylene Co., Ltd., Tafmer XM manufactured by Mitsui Chemicals, Inc., and Tafserene manufactured by Sumitomo Chemical Co., , Trade name LMPO manufactured by Idemitsu Retail Sales Co., Ltd., and the like.

The primer composition may contain a solvent. The solvent is preferably water, and may be a mixed solvent containing water and a hydrophilic organic solvent. Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve and butyl cellosolve, and ketones such as cyclohexanone. When the solvent contains a hydrophilic organic solvent, the percentage of the hydrophilic organic solvent to the whole solvent is preferably within a range of 0.1 to 50 mass%.

When the solvent is water or a mixed solvent containing water and a hydrophilic organic solvent of 50 mass% or less, it is preferable that the polyester resin and the modified polyolefin resin are dissolved in a solvent in the primer composition. In this case, the primer composition can be considered to be water-soluble.

The primer composition may contain a leveling agent. For example, when the solvent contains a hydrophilic organic solvent such as alcohol or glycol ether, the hydrophilic organic solvent may function as a leveling agent.

The primer composition may contain a crosslinking agent. The crosslinking agent may contain at least one member selected from the group consisting of, for example, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, and an epoxy crosslinking agent.

The primer composition may further contain suitable additives such as a defoaming agent, a film forming auxiliary, a pigment, and a dye.

The lamination member 1 in this embodiment will be described with reference to Fig. The lamination member 1 has a substrate 2, a primer layer 3 on the substrate 2, and an outer layer 4 on the primer layer 3. That is, the substrate 2, the primer layer 3, and the outer layer 4 are laminated in this order.

The shape of the substrate 2 is, for example, a plate shape, a sheet shape, or a film shape. Although the material of the base material 2 is not particularly limited, in this embodiment, even if the base material 2 is made of a non-polar material, adhesion between the base material 2 and the primer layer 3 is high

The base material 2 is, for example, a resin such as a thermoplastic resin or a metal such as a steel plate. The base material 2 is preferably a film made of a thermoplastic resin. Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate and polybutylene naphthalate; Polyhydroxycarboxylic acids such as polyglycolic acid and polylactic acid; Aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate); Polyamide resins such as nylon 6, nylon 66, and nylon 46; Polyolefin resins such as polypropylene, polyethylene, and ethylene-vinyl acetate copolymer; Polyimide resin; Polyarylate resins; And mixtures containing at least two of these resins. The substrate 2 is preferably made of a polyolefin resin, and particularly preferably made of a polypropylene resin.

The primer layer 3 can be formed on the substrate 2 by applying the primer composition to the substrate 2 and then drying the primer composition.

A method of forming the primer layer 3 when the base material 2 is a polyolefin resin film such as a polypropylene resin film will be described.

The polyolefin resin is dried and then melt-extruded to obtain an unoriented polyolefin resin sheet. The uniaxially stretched polyolefin resin film can be obtained by stretching the polyolefin resin sheet in one direction with a heating roll or the like. The biaxially oriented polyolefin resin film can be obtained by stretching the uniaxially stretched polyolefin resin film in the direction orthogonal to the above direction while heating, and then performing the heat treatment to complete the orientation.

By applying the primer composition to an unoriented polyolefin resin sheet, a uniaxially oriented polyolefin resin film or a biaxially oriented polyolefin resin film at any stage in the process of producing the biaxially oriented polyolefin resin film as described above, The layer 3 can be formed.

For example, the primer layer 3 can be formed by an off-line method. That is, after the biaxially oriented polyolefin resin film is completed, the primer layer 3 can be formed by applying the primer composition to the biaxially stretched polyolefin resin film and then drying the primer composition.

The primer layer 3 may be formed by an in-line method. That is, the primer layer 3 may be formed during the process of producing the biaxially oriented polyolefin resin film from the polyolefin resin. In this case, for example, a primer layer 3 is formed by applying a primer composition to an unstretched polyolefin resin sheet, followed by drying. Thereafter, the non-stretched polyolefin resin sheet is sequentially stretched in two directions, , A biaxially oriented polyolefin resin film can be produced. The primer layer 3 is formed by applying a primer composition to a uniaxially stretched polyolefin resin film and then dried to stretch the uniaxially stretched polyolefin resin film and heat treatment to obtain a biaxially oriented polyolefin resin film . &Lt; / RTI >

In the present embodiment, particularly when the primer composition is water-soluble, that is, when the solvent in the primer composition is water or a mixed solvent containing 50% by mass or less of water and a hydrophilic organic solvent, the primer layer 3 is formed from the primer composition The organic solvent does not volatilize or the amount of volatilization of the organic solvent is suppressed. Therefore, even if the solvent is volatilized from the primer composition in the process of producing the biaxially oriented polyolefin resin film from the polyolefin resin, the solvent is prevented from being ignited by heat during the stretching or heat treatment. Therefore, in any of the off-line method and the in-line method, the primer layer 3 can be formed from the primer composition while suppressing the danger of ignition.

Further, if the primer composition is an aqueous composition, it is environmentally friendly since the organic solvent is hardly released to the surrounding environment.

On the primer layer 3, an outer layer 4 of an appropriate resin or metal is formed. For example, as the outer layer 4, a layer comprising a photographic photosensitive layer, a diazo photosensitive layer, a mat layer, a magnetic layer, an inkjet ink receiving layer, a hard coating layer, an ultraviolet curable resin, a thermosetting resin, a printing ink, A thin film layer formed by vacuum deposition, electron beam deposition, sputtering, ion plating, CVD or plasma polymerization comprising an adhesive layer, a metal, an inorganic material or an oxide thereof by laminating or extrusion laminating, and an organic barrier layer. The primer layer 3 can obtain a good bonding strength with the outer layer 4 of various resins or metals.

In the present embodiment, the adhesion strength between the base material 2 and the primer layer 3 is high when the primer layer 3 is formed by forming the primer composition on the base material 2 made of resin or metal. The bonding strength between the primer layer 3 and the outer layer 4 when the outer layer 4 made of resin or metal is formed on the primer layer 3 is also high. However, the selectivity of the primer layer 3 at room temperature is low. For this reason, for example, if the metallic or resinous member is simply pressed and adhered to the primer layer 3, the member is hardly attached to the primer layer 3. For this reason, for example, the primer layer 3 may be attached to any member or the primer layer 3 may be formed between the formation of the primer layer 3 and the formation of the outer layer 4 on the primer layer 3 3) It is difficult to attach contaminants to the surface. Since the laminate member 1 has the base material 2 and the primer layer 3 but does not have the outer layer 4, even when the primer layer 3 is exposed to the outside, It is difficult to adhere to the member or adhere to the primer layer (3).

[Example]

[Preparation of polyester resin solutions A, B and C]

A stirrer, a nitrogen gas inlet, a thermometer, a rectification column, and a cooling condenser was prepared. The reaction vessel was charged with the raw materials described in each of column A, column B and column C in Table 1 to obtain a mixture. The mixture was heated to 200 ° C while stirring and mixing in a nitrogen atmosphere at atmospheric pressure, and then gradually heated to 250 ° C over 4 hours to complete the transesterification reaction. Subsequently, the mixture was gradually depressurized to a pressure of 0.67 hPa (0.5 mmHg) at a temperature of 250 DEG C, and then maintained in this state for 2 hours to proceed the polycondensation reaction. Thus, a polyester resin was obtained.

100 parts by mass of this polyester resin, 40 parts by mass of butyl cellosolve and 260 parts by mass of water were mixed and maintained under the temperature of 80 to 90 캜 for 2 hours while stirring to obtain a polyester resin having a polyester resin concentration of 25% Solution.

[Preparation of polyester resin solution D]

A stirrer, a nitrogen gas inlet, a thermometer, a rectification column, and a cooling condenser was prepared. In this reaction vessel, the materials except for trimellitic anhydride in the raw materials described in column D of Table 1 below were added to obtain a mixture. The mixture was heated to 200 캜 while stirring and mixing in a nitrogen atmosphere at atmospheric pressure, and then gradually heated to 250 캜 over 4 hours to complete the transesterification reaction. Next, trimellitic anhydride described in column D was added to this mixture, and the pressure was gradually reduced to 0.67 hPa (0.5 mmHg) at a temperature of 250 DEG C, and then maintained in this state for 2 hours to proceed the polycondensation reaction. Thus, a polyester resin was obtained.

100 parts by mass of this polyester resin, 40 parts by mass of butyl cellosolve, 255 parts by mass of water and 5 parts by mass of 25% by mass of ammonia water were mixed and kept under stirring at 80 to 90 ° C for 2 hours, To obtain a polyester resin solution having a resin concentration of 25 mass%.

[Preparation of polyester resin solution E]

A stirrer, a nitrogen gas inlet, a thermometer, a rectification column, and a cooling condenser was prepared. In this reaction vessel, the materials excluding the anhydrous pyromellitic acid in the raw materials described in column E of Table 1 below were added to obtain a mixture. The mixture was heated to 200 캜 while stirring and mixing in a nitrogen atmosphere at atmospheric pressure, and then gradually heated to 250 캜 over 4 hours to complete the transesterification reaction. Next, anhydrous pyromellitic acid as described in column E was added to the mixture, and the pressure was gradually reduced to 0.67 hPa (0.5 mmHg) at a temperature of 200 ° C, and then maintained in this state for 2 hours to proceed the polycondensation reaction. Thus, a polyester resin was obtained.

[Preparation of polyester resin solutions F and G]

A stirrer, a nitrogen gas inlet, a thermometer, a rectification column, and a cooling condenser was prepared. In this reaction vessel, except for anhydrous trimellitic acid in the raw materials described in each of column F and column G of Table 1 below, a mixture was obtained. The mixture was heated to 200 캜 while stirring and mixing in a nitrogen atmosphere at atmospheric pressure, and then gradually heated to 250 캜 over 4 hours to complete the transesterification reaction. Next, anhydrous trimellitic acid as described in each of F and G columns was added to the mixture, the pressure was gradually reduced to 0.67 hPa (0.5 mmHg) at a temperature of 250 DEG C, and then maintained for 2 hours in this state, Respectively. Thus, a polyester resin was obtained.

100 parts by mass of this polyester resin, 40 parts by mass of butyl cellosolve, 250 parts by mass of water and 10 parts by mass of 25% ammonia water were mixed and maintained at 80 to 90 캜 for 2 hours while stirring, To obtain a polyester resin solution having a resin concentration of 25 mass%.

[Table 1]

[Preparation of primer composition]

The polyester resin solution, the modified polyolefin resin solution and, if necessary, the additives were mixed in the solid content ratios shown in Tables 2 to 4 to obtain a mixed solution. And as a leveling agent, butyl cellosolve was added in an amount of 20 mass% with respect to the mixed solution to obtain a primer composition.

[evaluation]

· Preparation of primer layer

A polypropylene film not treated as a substrate was prepared. On this substrate, the primer composition was coated with a bar coater and then heated at 120 DEG C for 5 minutes. Thus, a primer layer having a thickness of about 1 mu m was formed on the substrate.

· Base Adhesion Test

A cellophane adhesive tape was closely adhered to the primer layer on the substrate and peeled off, and the state of the remaining primer layer was observed. As a result, it was evaluated as "A" when peeling of the primer layer was not recognized, "B" when peeling was observed in a part of the primer layer, and "C" when peeling was observed in most of the primer layers.

· Room temp test

As the member superimposed on the primer layer on the substrate, an untreated polypropylene film was prepared. The member and the primer layer were bonded at a temperature of 25 캜, a humidity of 60%, a pressing force of 0.1 MPa, and a pressing time of 1 hour under the condition that the member was superimposed on the primer layer. Subsequently, the tackiness at room temperature between the primer layer and the member was confirmed. As a result, the case where the tack is not recognized at the interface between the primer layer and the member is defined as " A ", the case where the tack is recognized at a part of the interface is defined as " B & I appreciated.

· Paint layer adhesion test

On the primer layer on the substrate, an acrylic resin-based aqueous white paint was applied by a bar coater and then heated at 120 캜 for 5 minutes. Thus, a coating layer having a thickness of about 2 mu m was formed on the primer layer. A cellophane adhesive tape was adhered to this paint layer and peeled off, and the state of the remaining paint layer was observed. As a result, it was evaluated as "A" when peeling of the paint layer was not recognized, "B" when peeling was observed in a part of the paint layer, and "C" when peeling was observed in most of the paint layer.

· Aluminum Vapor Deposition Adhesion Test

An aluminum deposition layer having a thickness of about 1 mu m was formed on the member having the primer layer formed thereon by a vacuum deposition process. The cellophane adhesive tape was adhered to and peeled from the aluminum vapor-deposited member, and the appearance of the remaining aluminum vapor-deposited layer was observed. As a result, the case where the peeling of the aluminum deposition layer was not recognized was referred to as " A ", the case where peeling was observed in a part of the aluminum deposition layer was defined as " B & I appreciated.

The modified polyolefin resin solution in the Tables is an aqueous dispersion of a maleic anhydride-modified polyolefin resin, the details of which are as follows.

APTOLOK BW-5550: manufactured by Mitsubishi Chemical Corporation, trade name APTOLOK BW-5550. An aqueous dispersion of a copolymer of a maleic anhydride-modified polypropylene and methoxypoly (oxyethylene / oxypropylene) -2-propylamine. Weight average molecular weight 135000.

Outloren AE-301: Outlorene AE-301, manufactured by Nippon Paper Industries Co., Ltd. An aqueous dispersion of maleic anhydride-acrylic-modified polyolefin resin. Weight average molecular weight 80000-100000.

Genpoly HGW9566: manufactured by LOTTE CHEMICAL CORPORATION, trade name Genpoly HGW9566. Aqueous dispersion of maleic anhydride-modified polypropylene resin. Weight average molecular weight of 40000 or more.

Details of additives in the tables are as follows.

Epocross WS-700: manufactured by Nippon Catalyst Co., Ltd., trade name Epochros WS-700, oxazoline crosslinking agent.

Carbodite SV-02: Carbodite SV-02, a carbodiimide type crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.

[Table 2]

[Table 3]

[Table 4]

As shown in the above table, in Examples 1 to 28, high adhesion was obtained between the primer layer and the substrate, the paint layer, and the aluminum vapor deposition layer.

On the other hand, in Comparative Examples 1 to 3 and 7 to 9, the adhesiveness between the primer layer and the substrate was maintained, but the adhesion between the primer layer and the aluminum deposition layer and the coating layer was deteriorated. This is because the proportion of the polyester resin in the primer composition is low, so that the polarity in the primer composition is reduced, and as a result, the adhesiveness with the base material made of polypropylene which is a non-polar material is maintained, It is presumed that the adhesiveness is lowered.

Further, in Comparative Examples 4 to 6 and 10 to 12, the adhesion of the primer layer to the substrate, the adhesion to the aluminum vapor deposition film, and the adhesion to the paint layer all decreased. The reason why the adhesion of the primer layer to the base material is lowered is that the proportion of the modified polyolefin resin in the primer composition is low and thus the number of non-polar regions in the primer composition becomes small. As a result, Which is the reason for the decrease in the amount of water. Further, in the adhesion test of the aluminum deposition layer and the paint layer, the aluminum deposition layer and the paint layer are easily peeled off from the base material in each primer layer, thereby presumably presuming that the adhesion between the aluminum deposition layer and the paint layer is apparently lowered do.

Claims

A polyester resin containing a polyvalent carboxylic acid residue and a glycol residue, and a modified polyolefin resin,
Wherein the polyvalent carboxylic acid residue comprises a polyvalent carboxylic acid residue comprising a metal sulfonate group,
The percentage of the polyvalent carboxylic acid residue containing the metal sulfonate group to the entire polyvalent carboxylic acid residue in the polyester resin is in the range of 1 to 60 mol%
Wherein the modified polyolefin resin contains an acid-modified polyolefin resin,
Wherein the mass ratio of the polyester resin to the modified polyolefin resin is in the range of 8/2 to 2/8.

The method according to claim 1,
Wherein the acid value of the polyester resin is in the range of 2 to 100 mgKOH / g.

3. The method according to claim 1 or 2,
Wherein the acid-modified polyolefin resin contains at least one of a maleic acid-modified polyolefin resin and a maleic anhydride-modified polyolefin resin.

3. The method according to claim 1 or 2,
Wherein the modified polyolefin resin is not chlorinated.

A base material,
And a primer layer formed on the base material and made from the hydrophilic primer composition described in any one of claims 1 and 2.

6. The method of claim 5,
And an outer layer made of metal or resin on the primer layer.

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