KR101825454B1 - Primer composition, stacked material, and method for producing primer composition - Google Patents

Abstract

The present invention provides a primer composition capable of forming a primer layer having high adhesiveness and transparency by being applied to a substrate. The primer composition contains a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is a product produced by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

Description

TECHNICAL FIELD [0001] The present invention relates to a primer composition, a lamination member, and a method for producing a primer composition,

More particularly, the present invention relates to a primer composition for forming a primer layer, a lamination member having a primer layer formed of the primer composition, and a method for producing the primer composition ≪ / RTI >

Various base materials, for example, polyolefin resin films such as polypropylene and polyethylene are coated with a metal vapor deposition layer in order to provide coatings, ink for printing, and gas barrier properties . 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 adhesive property improved by the surface treatment tends to deteriorate over time.

Thus, conventionally, in order to improve the adhesiveness of the base material, a primer having excellent adhesiveness is applied to the base material.

As such a primer, for example, Patent Document 1 discloses a primer comprising 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) composed of a copolymer comprising a monomer as a monomer, 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 ) Is disclosed.

In addition to high adhesiveness, the primer may be required to have high transparency. For example, when painting or the like is performed only on a part of the surface of the base material, or when coating or the like with high transparency is performed on the base material, the primer layer formed from the primer may be required to have high transparency.

International Publication WO2010 / 038643

An object of the present invention is to provide a primer composition capable of forming a primer layer having high adhesiveness and transparency by being applied to a substrate, a lamination member having a primer layer formed from the primer composition, and a method for producing the primer composition will be.

A primer composition according to one aspect of the present invention contains a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is a product produced by emulsion polymerization of the ethylenically unsaturated monomer (b) in a mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

A method for producing a primer composition according to one aspect of the present invention is a method for producing a primer composition, which comprises a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The method for producing the primer composition is a method for producing the above-mentioned polymerization reaction product (A) by emulsion polymerization of the ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b) , And mixing the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

According to one aspect of the present invention, there is provided a primer composition capable of forming a primer layer having high adhesiveness and transparency by being applied to a substrate, a lamination member having a primer layer formed from the primer composition, and a method for producing the primer composition Can be obtained.

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 is used, for example, to obtain the laminated member 1 as shown in Fig. The laminate member 1 comprises a substrate 2 and a primer layer 3 on the substrate 2 and containing a dried product of the primer composition and a metal or resin outer layer 4 on the primer layer 3 ).

The primer composition contains a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is a product produced by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mg KOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

The primer layer 3 can be formed on the base material 2 by applying the primer composition onto the base material 2 and then drying the primer composition. The primer layer 3 can have high adhesion with the base material 2 even if the base material 2 is a film made of a polyolefin resin such as polypropylene or polyethylene. The adhesion of the primer layer 3 to the base material 2 is realized by the maleic acid-modified polyolefin resin (B) in particular. When the outer layer 4 made of resin or metal is formed on the primer layer 3, the primer layer 3 can have high adhesion with the outer layer 4. High adhesion with the outer layer 4 of the primer layer 3 is realized particularly by the polymerization reaction product (A).

When the polymerization reaction product (A) is produced by emulsion polymerization of the ethylenically unsaturated monomer (b) in the mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) as described above, 3) can have high transparency.

It is presumed that the polymerization reaction product (A) is a mixture of the emulsion polymer of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b).

However, this embodiment is characterized in that the emulsion polymer of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is not just mixed, and that the polymerization reaction product (A) is produced by the aforementioned method . In the emulsion polymerization of the ethylenically unsaturated monomer (b), the saturated polyester resin (a) may function as an emulsifier. Thus, in the present embodiment, the polymerization reaction product (A) can contribute to the improvement of the transparency of the primer layer (3) and also to the improvement of the adhesion between the primer layer (3) and the outer layer (4).

In addition, since an emulsifier other than the saturated polyester resin (a) is not required in emulsion polymerization, it is possible not to include an emulsifier other than the saturated polyester resin (a) in the primer composition. Deterioration of the appearance and performance of the primer layer 3 due to bleeding out of the emulsifier from the primer layer 3 is suppressed when the primer composition contains no emulsifier other than the saturated polyester resin (a) .

Then, an ethylenically unsaturated monomer (b) is emulsion-polymerized by using an emulsifying agent other than the saturated polyester resin (a) to synthesize a polymer, and this polymer is mixed with a saturated polyester resin (a), a maleic acid-modified polyolefin resin ) And water (C), the transparency of the layer formed from this composition is lower than the transparency of the primer layer 3 according to the present embodiment. Furthermore, the adhesion between the layer formed from this composition and the outer layer 4 is lower than the adhesion of the primer layer 3 according to the present embodiment. That is, the composition and the layer described above and the primer composition and the primer layer 3 according to the present embodiment differ in the product itself. However, even when the inventors analyzed both of them by the infrared absorption method and the high-performance liquid chromatography method, no significant difference was recognized between the results of both analyzes. Therefore, the structure or properties of the polymerization reaction product (A) can not be specified by words.

The components of the primer composition will be described in more detail.

The saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2).

The polyvalent carboxylic acid residue (a1) can be obtained, for example, from a polyvalent carboxylic acid residue (a11) having three or more valences, a polyvalent carboxylic acid residue (a12) having a metal sulfonate group and a dicarboxylic acid residue And at least one kind of group selected from the group consisting of

The polyvalent carboxylic acid residue (a11) having a trivalent or higher valence is, for example, at least one selected from the group consisting of a hemimellitic acid residue, a trimellitic acid residue, a trimesic acid residue, a melomenate residue, a pyromellitic acid residue, a benzenepentacarboxylic acid residue, At least one group selected from the group consisting of cyclopropane-1,2,3-tricarboxylic acid residue, cyclopentane-1,2,3,4-tetracarboxylic acid residue, and ethanetetracarboxylic acid residue.

The polyvalent carboxylic acid residue (a12) having a metal sulfonate group is, for example, a dicarboxylic acid residue having a metal sulfonate group. More specifically, the polyvalent carboxylic acid residue (a12) may be, for example, a 5-sulfoisophthalic acid residue, a 2-sulfoisophthalic acid residue, a 4-sulfoisophthalic acid residue, a 2-sulfoterephthalic acid residue, -Sulfonaphthalene-2,6-dicarboxylic acid residue, and a sulfone naphthalene-2,6-dicarboxylic acid residue.

The dicarboxylic acid residue (a13) contains, for example, at least one of an aromatic dicarboxylic acid residue and an aliphatic dicarboxylic acid residue. 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, , A 5-naphthalene dicarboxylic acid residue, and a 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 isomer residue, an azela residue, a sebacic acid residue, a dodecanedioic acid residue, a 1,3-cyclopentanedicarboxylic acid residue, a 1,4-cyclohexanedicarboxylic acid residue, 1,3-cyclohexanedicarboxylic acid residue, 1,2-cyclohexanedicarboxylic acid residue, 1,2-cyclopropanedicarboxylic acid residue, 1,2-cyclobutanedicarboxylic acid residue, diglycolic acid residue, and Thiodipropionic acid residue and thiodipropionic 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, an adipic acid residue, a sebacic acid residue, a 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. In particular, it is preferable that the aromatic dicarboxylic acid residue and the 1,4-cyclohexanedicarboxylic acid residue are the main components of the polyvalent carboxylic acid residue (a1).

The polyvalent carboxylic acid residue (a1) preferably contains a trivalent or more polyvalent carboxylic acid residue (a11). In this case, the saturated polyester resin (a) may have a carboxyl group derived from a trivalent or more polyvalent carboxylic acid residue (a11). For this reason, the saturated polyester resin (a) can effectively function as an emulsifier, and at the same time, the saturated polyester resin (a) can have high water-solubility or water-dispersibility. Further, the saturated polyester resin (a) can impart high adhesion to the primer layer 3 with the base material 2 and the outer layer 4.

The amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is preferably within a range of 1 to 50 mol%. When the amount of the polyvalent carboxylic acid residue (a11) is within the range of 1 to 50 mol%, the saturated polyester resin (a) functions particularly effectively as an emulsifier, and the saturated polyester resin (a) And the saturated polyester resin (a) can impart particularly high adhesiveness to the primer layer (3). The amount of the polyvalent carboxylic acid residue (a11) is more preferably 5 mol% or more, and more preferably 10 mol% or more. The amount of the polyvalent carboxylic acid residue (a11) is more preferably 45 mol% or less, and further preferably 40 mol% or less.

The polyvalent carboxylic acid residue (a1) may contain a polyvalent carboxylic acid residue (a12) having a metal sulfonate group. In this case, the saturated polyester resin (a) may have a metal sulfonate group which is a polar group derived from the polyvalent carboxylic acid residue (a12). Therefore, the saturated polyester resin (a) has particularly high water-solubility or water dispersibility, and the polymerization reaction product (A) can impart particularly high adhesion to the primer layer (3).

However, in order to impart a high water resistance to the primer layer 3, the amount of the polyvalent carboxylic acid residue (a12) relative to the polyvalent carboxylic acid residue (a1) is preferably 3 mol% or less, more preferably 1 mol% Do.

It is also preferable that the polycarboxylic acid residue (a1) contains an alicyclic polycarboxylic acid residue (a10). In this case, the primer layer 3 can have particularly high transparency.

The alicyclic polycarboxylic acid residue (a10) is, for example, 1,4-cyclohexanedicarboxylic acid residue, 1,3-cyclopentanedicarboxylic acid residue, 1,3-cyclohexanedicarboxylic acid residue, At least one kind of group selected from the group consisting of a 2-cyclohexanedicarboxylic acid residue, a 1,2-cyclopropanedicarboxylic acid residue, and a 1,2-cyclobutanedicarboxylic acid residue.

The amount of the alicyclic polycarboxylic acid residue (a10) relative to the polycarboxylic acid residue (a1) is preferably within a range of 30 to 99 mol%. When the amount of the alicyclic polycarboxylic acid residue (a10) is 30 mol% or more, the primer layer 3 can have particularly high transparency. The content of the alicyclic polycarboxylic acid residue (a10) is more preferably 40 mol% or more.

The glycol residue (a2) may be, for example, an ethylene glycol residue, a diethylene glycol residue, a triethylene glycol residue, a tetraethylene glycol residue, a pentaethylene glycol residue, a hexaethylene glycol residue, a heptaethylene glycol residue, Of polyethylene glycol residues; 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 (a2) is preferably an ethylene glycol residue; 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 a bisphenol A residue, in addition to the above-mentioned monomers. In this case, the synthesis of the saturated polyester resin (a) is easy, and the saturated polyester resin (a) can have high durability.

It is also preferable that the glycol moiety (a2) contains an alicyclic glycol moiety (a20). In this case, the primer layer 3 can have particularly high transparency.

The alicyclic glycol moiety (a20) is at least one selected from the group consisting of 1,4-cyclohexane dimethanol residue, 1,2-cyclobutane dimethanol residue, and 1,2-cyclopropane dimethanol residue It contains one kind of group.

The amount of the alicyclic glycol residue (a20) relative to the glycol residue (a2) is preferably within a range of 30 to 100 mol%. When the amount of the alicyclic glycol moiety (a20) is 30 mol% or more, the primer layer 3 can have particularly high transparency. The amount of the alicyclic glycol moiety (a20) is more preferably 40 mol% or more.

The glycol residue (a2) preferably contains no trivalent or more glycol residue. When the glycol residue (a2) contains a trivalent or higher-valent glycol residue, the amount of the trivalent or higher-valent glycol residue relative to the glycol residue (a2) is preferably 1 mol% or less. In this case, since the presence of excessive crosslinking in the saturated polyester resin (a) is suppressed, the saturated polyester resin (a) can have higher water solubility or water dispersibility.

As described above, the saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g. Therefore, the saturated polyester resin (a) effectively functions as an emulsifier, the saturated polyester resin (a) has a particularly high water-solubility or water dispersibility, and the polymerization reaction product (A) Particularly high adhesion can be imparted. The acid value of the saturated polyester resin (a) can be controlled, for example, by adjusting the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1). In order for the saturated polyester resin (a) to function particularly effectively as an emulsifier, the acid value of the saturated polyester resin (a) is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more. Further, the acid value is preferably 95 mgKOH / g or less, more preferably 90 mgKOH / g or less.

The weight average molecular weight of the saturated polyester resin (a) is preferably in the range of 3000 to 50000. If the weight average molecular weight is 3000 or more, the primer layer 3 can have particularly high adhesiveness. When the weight average molecular weight is 50,000 or less, the saturated polyester resin (a) may have particularly high water solubility or water dispersibility. The weight average molecular weight is more preferably 4000 or more, and more preferably 5000 or more. The weight average molecular weight is more preferably 30,000 or less, and even more preferably 20,000 or less. The weight average molecular weight of the saturated polyester resin (a) is easily adjusted by suitably setting the conditions for the synthesis of the saturated polyester resin (a). The weight average molecular weight of the saturated polyester resin (a) is a value measured by gel permeation chromatography (in terms of polystyrene).

The glass transition temperature of the saturated polyester resin (a) is preferably in the range of 0 to 80 캜. If the glass transition temperature is 0 占 폚 or higher, the primer layer 3 can be prevented from having an excessively high tackiness. When the glass transition temperature is 80 캜 or lower, good moldability can be obtained when the primer layer 3 is formed from the primer composition. The glass transition temperature is more preferably 10 ° C or higher, and more preferably 15 ° C or higher. The glass transition temperature is more preferably 70 DEG C or lower, and more preferably 65 DEG C or lower.

The saturated polyester resin (a) 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. Examples of the ester-forming functional group include 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 the 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 groups obtained by anhydride-forming a carboxyl group, groups obtained by esterifying a carboxyl group, groups obtained by acidifying a carboxyl group, and groups obtained by halogenating a carboxyl group. The ester-forming inducible group of a hydroxyl group is a group which is obtained by reacting a compound with a hydroxyl group and is able to react with a carboxyl group to form an ester bond. Specific examples of the ester-forming inducible group of the 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 in the production of the saturated polyester resin (a) becomes favorable.

The reactive raw material contains a polyvalent carboxylic acid component corresponding to the polyvalent carboxylic acid residue (a1) in the saturated polyester resin (a) and a glycol component corresponding to the glycol residue (a2) in the saturated polyester resin (a). The polyvalent carboxylic acid component contains 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 contains at least one compound selected from the group consisting of an ester-forming derivative of a glycol and 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 saturated polyester resin (a) is synthesized from a reactive raw material by a known polyester production method. For example, the saturated polyester resin (a) is synthesized by a direct esterification reaction in which the polyvalent carboxylic 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 a glycol, the first stage reaction, which is an ester exchange reaction between an ester-forming derivative of a polyvalent carboxylic acid and a glycol, The saturated polyester resin (a) 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 some 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 up to 150 to 260 占 폚 under atmospheric pressure in an inert gas atmosphere such as nitrogen gas, The transesterification reaction proceeds. 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 stage reaction and the second stage reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds and the like may be added as a catalyst in the reaction system at any time.

Further, since the ethylenically unsaturated monomer (b) contains the nonionic ethylenically unsaturated monomer (b1), the polymerization reaction product (A) can have particularly high water dispersibility and dispersion stability.

The nonionic ethylenic unsaturated monomer (b1) contains, for example, a (meth) acrylic acid ester. More specifically, the nonionic ethylenic unsaturated monomer (b1) is, for example, methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylate, isobutyl acrylate, 2-ethylhexyl (meth) acrylate, styrene, cyclohexyl (meth) acrylate, tert-butyl (meth) acrylate, 3-hydroxypropyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, stearyl (meth) acrylate, and octyl (meth) acrylate. The term "(meth) acrylate" means at least one of acrylic and methacrylic. For example, "(meth) acrylic acid ester" means at least one of an acrylic acid ester and a methacrylic acid ester.

The nonionic ethylenic unsaturated monomer (b1) preferably contains a monomer (b0) having a hydroxyl group. In this case, since the primer layer 3 can have a hydroxyl group derived from the monomer b0, the primer layer 3 has a higher polarity than the base 2 and the outer layer 4, It may have adhesion.

Examples of the monomer (b0) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Butyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol .

The amount of the monomer (b0) relative to the ethylenically unsaturated monomer (b) is preferably within a range of 1 to 40 mol%. When the amount of the monomer b0 is 1 mol% or more, the primer layer 3 can have particularly high adhesion with the highly polar base material 2 and particularly high adhesion with the outer polar layer 4 having a high polarity. When the amount of the monomer (b0) is 40 mol% or less, the polymerization reaction product (A) can have particularly high water dispersibility and dispersion stability. The amount of the monomer (b0) is more preferably 5 mol% or more, and more preferably 10 mol% or more. The amount of the monomer (b0) is more preferably 30 mol% or less, and more preferably 25 mol% or less.

The ethylenically unsaturated monomer (b) consists, for example, only of the nonionic ethylenically unsaturated monomer (b1).

The polymerization reaction product (A) is synthesized by emulsion polymerization of the ethylenically unsaturated monomer (b) using the saturated polyester resin (a) as an emulsifier as described above. More specifically, first, for example, an aqueous solution containing the saturated polyester resin (a) is prepared. The amount of the saturated polyester resin (a) relative to the aqueous solution is, for example, in the range of 5 to 50 mass%. The aqueous solution is heated to a temperature within a range of, for example, 60 to 100 占 폚, and at the same time, the polymerization initiator is introduced into the aqueous solution while stirring. The ethylenically unsaturated monomer (b) is added to the aqueous solution while maintaining the aqueous solution at a temperature within the range of 60 to 100 占 폚 while stirring. The aqueous solution is maintained at a temperature within a range of 60 to 100 占 폚 for 60 to 300 minutes while stirring, for example, and the emulsion polymerization proceeds. Thereby, the polymerization reaction product (A) can be synthesized, and as a result, an aqueous dispersion solution containing the polymerization reaction product (A) can be obtained.

In the synthesis of the polymerization reaction product (A), a polymer having at least one of a carboxyl group and a hydroxyl group may be added to the reaction system at any time as a component for improving the water dispersibility of the polymerization reaction product (A) . This polymer may be, for example, a group consisting of an acrylate polymer, a methacrylate polymer, a styrene-acrylate polymer, a styrene-methacrylate polymer, a styrene-maleate polymer, a styrene-maleic anhydride polymer, and a polyvinyl alcohol And the like.

The mass ratio of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is preferably in the range of 99: 1 to 10:90. In this case, the dispersibility of the polymerization reaction product (A) in the aqueous dispersion obtained by synthesizing the polymerization reaction product (A) can be particularly high, and the dispersibility of the polymerization reaction product (A) in the primer composition can be particularly high have. In addition, the primer layer 3 can have particularly high transparency. This mass ratio is more preferably in the range of 90:10 to 20:80, and still more preferably in the range of 80:20 to 30:70.

The maleic acid-modified polyolefin resin (B) may include a maleic anhydride-modified polyolefin resin. The maleic acid-modified polyolefin resin (B) may contain a resin obtained by modifying the polyolefin resin with at least one of maleic acid and maleic anhydride.

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, ≪ / RTI > compounds.

The maleic acid-modified polyolefin resin (B) is, for example, a copolymer of at least one of maleic acid and maleic anhydride with an alkene. In this copolymer, at least one of maleic acid and maleic anhydride and the alkene may be randomly copolymerized, block copolymerized, or graft copolymerized.

Specific examples of the maleic acid-modified polyolefin resin (B) include trade name Aurorene manufactured by Japan Paper Manufacturing Co., Ltd., product name APTOLOK manufactured by Mitsubishi Kagaku Kogyo Co., Ltd., product name GENPOLY manufactured by LOTTE CHEMICAL CORPORATION, Manufactured by Sumitomo Chemical Co., Ltd., trade name: Hiruren, manufactured by Sumitomo Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., trade name Super Clone, manufactured by Japan Paper Manufacturing Co., Ltd., trade name: WINTECH manufactured by NIPPON POLYPROPYLENE INDUSTRIES, TMPERM XM, manufactured by Sumitomo Chemical Co., Ltd., and TMPTA, manufactured by Sumitomo Chemical Co., Ltd., and LMPO, manufactured by Idemitsu Retail Sales &

The maleic acid-modified polyolefin resin (B) has a non-polar polyolefin skeleton. For this reason, the primer layer 3 can have high adhesiveness with a non-polar material such as polyolefin. Further, since the maleic acid-modified polyolefin resin (B) is modified to at least one of maleic acid and maleic anhydride, it also has a portion having polarity. Accordingly, the maleic acid-modified polyolefin resin (B) can have a high dispersibility in the primer composition.

The mass ratio of the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B) is preferably within a range of 80:20 to 20:80. In this case, the primer layer 3 can have particularly high adhesiveness with a non-polar material such as polyolefin.

Water (C) is a solvent or dispersion medium in the primer composition.

The primer composition may contain, as a solvent or a dispersion medium, a hydrophilic organic solvent together with water (C). 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 primer composition contains a hydrophilic organic solvent, the amount of the hydrophilic organic solvent relative to the total amount of the water (C) and the hydrophilic organic solvent is preferably within a range of 0.1 to 50 mass%.

The primer composition may contain a leveling agent. For example, when the primer composition 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 contain another resin aqueous dispersion. The other resin water dispersion may contain, for example, at least one member selected from the group consisting of a urethane resin aqueous dispersion, an acrylic resin aqueous dispersion, a polyester resin aqueous dispersion, and an olefin resin aqueous dispersion.

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

The method for producing a primer composition according to the present embodiment is a method for producing a primer composition containing a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C) (A) is obtained by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing an ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (b), and a polymerization reaction product B). The production method includes, for example, synthesizing a polymerization reaction product (A) by using a saturated polyester resin (a) as an emulsifier and emulsion polymerization of a nonionic ethylenically unsaturated monomer (b) (A) and the maleic acid-modified polyolefin resin (B).

The method of synthesizing the polymerization reaction product (A) and the method of obtaining the aqueous dispersion containing the polymerization reaction product (A) are as described above. The water in the aqueous dispersion may be water (C) in the primer composition as it is, but water may be further added to the aqueous dispersion to adjust the amount of water (C) in the primer composition.

The lamination member 1 according to the present embodiment will be described. 1, the lamination member 1 is provided with a base material 2 and a primer layer 3 on the base material 2. [ The primer layer (3) contains a dried product of the primer composition. In the present embodiment, the laminate member 1 further comprises an outer layer 4 made of metal or resin 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 base material 2 is, for example, a plate, sheet or film. Even if the base material 2 is made of a non-polar material, the adhesion between the base material 2 and the primer layer 3 is high.

The base material 2 is made of, for example, a resin such as a thermoplastic resin or is made of a metal such as a steel sheet. 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 comprising at least two of these resins. The substrate 2 is preferably made from a polyolefin resin, and is particularly preferably made from a polypropylene resin.

For example, the primer layer 3 can be produced on the substrate 2 by applying the primer composition to the substrate 2 and then drying the primer composition.

A method of producing the primer layer 3 in the case where the substrate 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 produce an unoriented polyolefin resin sheet. This polyolefin resin sheet is stretched in one direction with a heating roll or the like to produce a uniaxially stretched polyolefin resin film. Further, the uniaxially stretched polyolefin resin film is stretched in the direction orthogonal to the above direction while heating, and then the orientation is completed by performing heat treatment to produce a biaxially oriented polyolefin resin film.

The primer composition is applied to an unstretched polyolefin resin sheet, a uniaxially stretched polyolefin resin film or a biaxially stretched polyolefin resin film at any stage in the process of producing the biaxially stretched polyolefin resin film, 3) can be produced.

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

The primer layer 3 may be produced by an in-line method. That is, the primer layer 3 may be produced 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 prepared by applying a primer composition to an unoriented polyolefin resin sheet, followed by drying, and then the unstretched polyolefin resin sheet is sequentially stretched in two directions, , A biaxially oriented polyolefin resin film can be produced. The primer layer 3 is prepared by applying a primer composition to a uniaxially stretched polyolefin resin film and then dried, and then the uniaxially stretched polyolefin resin film is stretched and subjected to heat treatment to obtain a biaxially oriented polyolefin resin film . ≪ / RTI >

In this embodiment, since the primer composition contains water (C) as a solvent or a dispersion medium, the organic solvent does not volatilize or the volatilization amount of the organic solvent is suppressed in the process of producing the primer layer (3) do. Therefore, there is a low risk that the organic solvent will ignite during the stretching and heat treatment in the process of producing the biaxially oriented polyolefin resin film from the polyolefin resin. Therefore, in any of the off-line method and the in-line method, the primer layer 3 can be produced from the primer composition while suppressing the danger of ignition.

Further, when the primer composition contains water (C) as a solvent or a dispersion medium, it is environmentally friendly since it is difficult for the organic solvent to be released from the primer composition to the surrounding environment.

On the primer layer 3, an outer layer 4 of a suitable resin or metal may be produced. The outer layer 4 may be, for example, a photographic photosensitive layer; A diazo photosensitive layer; A mat layer; A magnetic layer; An inkjet ink receiving layer; Hard coating layer; A paint layer; A layer made of an ultraviolet curing resin, a thermosetting resin, a printing ink, a UV ink or the like; An adhesive layer by dry lamination or extrusion lamination; Vacuum deposition comprising a metal, an inorganic material, or an oxide thereof; A thin film layer formed by electron beam deposition, sputtering, ion plating, CVD or plasma polymerization; Or an organic barrier layer. The primer layer (3) can have high adhesiveness with the outer layer (4) made of various resins or metals.

[Example]

(1) Preparation of Samples A to G

Samples A to G which were aqueous dispersions containing a saturated polyester resin were prepared as follows.

A stirrer, a nitrogen gas inlet, a thermometer, a rectification column, and a cooling condenser was prepared. In this reaction vessel, components except for trimellitic anhydride in the column of "raw material component of saturated polyester resin" in Tables 1 and 2 were added to obtain a mixture. These were heated to 200 DEG C while stirring and mixing in an atmospheric pressure and a nitrogen atmosphere, and then gradually heated to 250 DEG C over 4 hours to complete the esterification reaction and the transesterification reaction. Next, anhydrous trimellitic acid in the column of "raw material component of the saturated polyester resin" in Tables 1 and 2 was added to this mixture, and the pressure was gradually reduced to 0.67 hPa (0.5 mmHg) at 230 ° C., For 2 hours to proceed a polycondensation reaction, thereby synthesizing a saturated polyester resin.

Saturated polyester resin, isopropyl alcohol, 25% ammonia water, and water were placed in a vessel at mass ratios shown in the column of "sample composition" in Tables 1 and 2. These were kept under stirring at a temperature of 75 to 85 캜 for 2 hours to obtain an aqueous dispersion having a saturated polyester resin concentration of 25 mass%.

The weight average molecular weight, glass transition temperature, and acid value of the saturated polyester resin are as shown in Tables 1 and 2.

[Table 1]

[Table 2]

(2) Preparation of Samples A-1 to G-1

Samples A-1 to G-1, which were aqueous dispersions containing a polymerization reaction product, were prepared as follows.

A reaction vessel having a capacity of 2000 ml and equipped with a stirrer, a nitrogen gas inlet, a thermometer, a dropping funnel and a reflux condenser was prepared. To this reaction vessel, the components shown in the column of "Saturated polyester resin water dispersion" And the mixture was heated to 80 DEG C while stirring in a nitrogen gas atmosphere. Next, 2 parts by mass of an aqueous ammonium persulfate solution having a concentration of 5% by mass was charged as a polymerization initiator into the reaction vessel, and then the content of the reaction vessel was charged into the reaction vessel under the column of "ethylenically unsaturated monomer" in Tables 3 and 4 The components shown were added dropwise over 2 hours. Next, 2 parts by mass of an aqueous ammonium persulfate solution having a concentration of 5% by mass was added to the reaction vessel, and the contents of the reaction vessel were stirred and maintained at a temperature of 80 캜 for 3 hours to synthesize an emulsion polymer.

At the time of preparing the sample B-2, 50 parts by mass of an aqueous acrylic resin dispersion liquid having a concentration of 20% by mass was added to the contents of the reaction vessel. The acrylic resin water dispersion was prepared by maintaining 100 parts by mass of an acrylic resin (trade name: Joncryl 680, manufactured by BASF), 25 parts by mass of 25% ammonia water and 375 parts by mass of water at a temperature of 75 to 85 캜 with stirring for 2 hours .

Further, at the time of preparing Sample C-3, 100 parts by mass of a 20% by mass concentration styrene maleic anhydride copolymer aqueous dispersion was added to the contents of the reaction vessel. At the time of preparing the sample F-1, 50 parts by mass of a 20% by mass concentration styrene maleic anhydride copolymer aqueous dispersion was added to the contents of the reaction vessel. The styrene maleic anhydride copolymer aqueous dispersion was prepared by mixing 100 parts by mass of styrene maleic anhydride copolymer (trade name: SMA 1440, manufactured by Clay Valley), 25 parts by mass of 25% ammonia water, and 375 parts by mass of water, At a temperature of 40 DEG C for 2 hours.

Thus, an aqueous dispersion liquid containing the polymerization reaction product was obtained.

The column of "mass ratio of the saturated polyester resin and the ethylenically unsaturated monomer" in Tables 3 and 4 shows the mass ratio of the saturated polyester resin to the ethylenically unsaturated monomer in the aqueous dispersion of the saturated polyester resin.

[Table 3]

[Table 4]

(3) Preparation of sample A-mix

A sample A-mix was prepared as follows.

A reaction vessel having a capacity of 1000 ml and equipped with a stirrer, a nitrogen gas inlet, a thermometer, a dropping funnel and a reflux condenser was prepared, and 240 parts by mass of ion-exchanged water and 5 parts by mass of sodium laurylsulfate were charged into the reaction vessel. Lt; RTI ID = 0.0 > 80 C < / RTI > Next, 2 parts by mass of an aqueous ammonium persulfate solution having a concentration of 5% by mass as a polymerization initiator was added to the reaction vessel and while stirring the contents of the reaction vessel, 60 parts by mass of methyl methacrylate and 40 parts by mass of butyl methacrylate were added to the reaction vessel over 2 hours Lt; / RTI > Next, 2 parts by mass of an aqueous ammonium persulfate solution having a concentration of 5% by mass was added to the reaction vessel, and the contents of the reaction vessel were stirred and maintained at a temperature of 80 캜 for 3 hours to prepare an aqueous dispersion of emulsified polymer.

The aqueous dispersion of the emulsion polymerizate and the sample A were mixed so that the mass ratio of the saturated polyester resin in the sample A to the total amount of methyl methacrylate and butyl methacrylate used in the synthesis of the emulsion polymerizate was 1: A-mix was obtained.

(4) Preparation of sample C-mix

A sample C-mix was prepared as follows.

A reaction vessel having a capacity of 1000 ml and equipped with a stirrer, a nitrogen gas inlet, a thermometer, a dropping funnel and a reflux condenser was prepared, and 240 parts by mass of ion-exchanged water and 5 parts by mass of sodium laurylsulfate were charged into the reaction vessel. Lt; RTI ID = 0.0 > 80 C < / RTI > Subsequently, 2 parts by mass of an aqueous ammonium persulfate solution having a concentration of 5% by mass was introduced as a polymerization initiator into the reaction vessel, and while stirring the contents of the reaction vessel, 40 parts by mass of methyl methacrylate and 40 parts by mass of butyl methacrylate And 20 parts by mass of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. Next, 2 parts by mass of an aqueous ammonium persulfate solution having a concentration of 5% by mass was added to the reaction vessel, and the contents of the reaction vessel were stirred and maintained at a temperature of 80 캜 for 3 hours to prepare an aqueous dispersion of emulsified polymer.

The aqueous dispersion of the emulsion polymerizate and the mass ratio of the sample C to the total amount of methyl methacrylate, butyl methacrylate and 2-hydroxyethyl methacrylate used in the synthesis of the saturated polyester resin and emulsion polymer in the sample C 3: 2, thereby obtaining a sample C-mix.

(5) Preparation of Examples 1 to 19 and Comparative Examples 1 to 4

Examples 1 to 19 and Comparative Examples 1 to 4, which are primer compositions, were prepared as follows.

The components shown in the column of " aqueous dispersion containing the polymerization reaction product " in Tables 5 and 6 and the components shown in the column of " modified polyolefin resin solution " were mixed. In the preparation of Examples 11, 17 and 19, Were further mixed to obtain a mixed solution. To this mixed solution, a butylcellosolve aqueous solution having a concentration of 30 mass% as a leveling agent was added to obtain a primer composition having a solid content concentration of 25 mass%.

The components shown in the column of the " modified polyolefin resin solution " in Tables 5 and 6 are aqueous dispersions of the maleic acid-modified polyolefin resin, the details of which are as follows.

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.

Aurora AE-301: Aurora 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.

Aurora AE-501: Aurora AE-501, manufactured by Nippon Paper Industries Co., Ltd. Aqueous dispersion of maleic anhydride-modified polyolefin resin, weight average molecular weight of 100,000 to 1500,000.

APTOLOK BW-5550: manufactured by Mitsubishi Kagaku Co., Ltd., trade name APT0L0K 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.

Details of the components shown in the column of " additive " in Tables 5 and 6 are as follows.

Epocross WS-700: water-soluble polymer containing oxazoline group, product name: Epochros WS-700, manufactured by Japan Catalyst Co., Ltd.

Carbodite SV-02: An aqueous cross-linking agent having a hydrophilic segment added to a polycarbodiimide resin, Carbodite SV-02, manufactured by Nisshinbo Chemical Co., Ltd.

(6) Property test

The following tests were carried out on the primer compositions Examples 1 to 19 and Comparative Examples 1 to 4.

(6-1) Preparation of primer layer

An untreated polypropylene film was prepared as a substrate. 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 1 m was formed on the substrate.

(6-2) Hayes

Only in the case of this haze test, a primer layer having a thickness of 3 占 퐉 was formed using a polyethylene terephthalate film (manufactured by Toray Industries, Ltd., trade name: Lumirra T60 # 100) as a base material. Then, the haze of the substrate alone and the haze of the base material and the primer layer were measured using a haze meter NDH 2000 manufactured by NIPPON FOKEN INDUSTRIAL CO., LTD. The haze of the primer layer was calculated by subtracting the haze of the substrate only from the haze of the base material and the primer layer.

(6-3) At room temperature tack

An untreated polypropylene film was prepared as a member superimposed on the primer layer on the substrate. 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 this 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 was not recognized at the interface between the primer layer and the member was defined as " A ", the case where the tack was recognized at a part of the interface was defined as " B & Respectively.

(6-4) Base adhesive property

A cellophane adhesive tape was closely adhered to the primer layer on the substrate and peeled off to observe the state of the remaining primer layer. As a result, "A" indicates that the peeling of the primer layer is not recognized, "B" indicates that peeling can be observed in only a part of the primer layer, "C" D "in the case where peeling was recognized in most of the cases.

(6-5) Paint Layer Adhesiveness

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 2 占 퐉 was formed on the primer layer. The cellophane adhesive tape was closely adhered to the coating layer and peeled off to observe the state of the remaining coating layer. As a result, the case where peeling of the paint layer was not recognized was designated as "A", the case where peeling was recognized from a very small part of the paint layer was referred to as "B", the case where peeling was recognized in a part of the paint layer as "C" D "in the case where peeling was recognized in most of the cases.

(6-6) Aluminum vapor deposition layer adhesion

An aluminum vapor deposition layer having a thickness of about 1 m was formed on the primer layer on the substrate by a vacuum deposition process. A cellophane adhesive tape was adhered to the aluminum vapor-deposited layer and peeled off to observe the state of the remaining aluminum vapor-deposited layer. As a result, the case where peeling of the aluminum deposition layer was not recognized was defined as " A ", the case where peeling was observed in a very small part of the aluminum deposition layer was indicated as " B &Quot; D " when peeling was observed in most of the aluminum deposition layer.

[Table 5]

[Table 6]

As apparent from the above-described embodiments, the primer composition according to the first aspect contains the polymerization reaction product (A), the maleic acid-modified polyolefin resin (B), and water (C). The polymerization reaction product (A) is a product produced by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mg KOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

In the primer composition according to the second aspect, the mass ratio of the polymerization reaction product (A) and the maleic acid-modified polyolefin resin (B) in the first aspect is within a range of 80:20 to 20:80.

In the primer composition according to the third aspect, in the first or second aspect, the saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2) Contains a polyvalent carboxylic acid residue (a11) having three or more valences, and the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is within a range of 1 to 50 mol%.

In the primer composition according to the fourth aspect, in the third aspect, the polyvalent carboxylic acid residue (a1) contains an alicyclic polyvalent carboxylic acid residue (a10) and the alicyclic polyvalent aliphatic carboxylic acid residue The amount of the carboxylic acid residue (a10) is in the range of 30 to 99 mol%.

In the primer composition according to the fifth aspect, in the third or fourth aspect, the glycol residue (a2) contains the alicyclic glycol residue (a20) and the alicyclic glycol residue (a20 ) Is in the range of 30 to 100 mol%.

In the primer composition according to the sixth aspect, in the first to fifth aspects, the mass ratio of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is within the range of 99: 1 to 10:90.

In the primer composition according to the seventh aspect, in the first to sixth aspects, the nonionic ethylenic unsaturated monomer (b1) contains a monomer (b0) having a hydroxyl group, and the nonionic ethylenic unsaturated monomer (b1) The amount of the monomer (b0) having a hydroxyl group is within a range of 1 to 40 mol%.

The lamination member according to the eighth aspect comprises a base material and a primer layer on the base material, and the primer layer contains a dried product of the primer composition according to any one of the first to seventh aspects.

The ninth aspect of the lamination member according to the eighth aspect is provided with an outer layer made of metal or resin on the primer layer.

The method for producing a primer composition according to the tenth aspect is a method for producing a primer composition, which comprises a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B), and water (C). This production method is characterized in that a polymerization reaction product (A) is synthesized by emulsion polymerization of an ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b) And mixing the product (A) and the maleic acid-modified polyolefin resin (B). The saturated polyester resin (a) has an acid value in the range of 10 to 100 mg KOH / g. The ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1).

The method for producing a primer composition according to an eleventh aspect is the method for producing a primer composition according to the eleventh aspect, wherein the saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2) Contains a polyvalent carboxylic acid residue (a11) having three or more valences, and the amount of the polyvalent carboxylic acid residue (a11) with respect to the polyvalent carboxylic acid residue (a1) is within a range of 1 to 50 mol%.

Claims (11)

(A), a maleic acid-modified polyolefin resin (B), and water (C)
The polymerization reaction product (A) is a product produced by emulsion polymerization of the ethylenically unsaturated monomer (b) in a mixture containing the saturated polyester resin (a) and the ethylenically unsaturated monomer (b)
The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g,
Wherein the ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1). The method according to claim 1,
Wherein the mass ratio of the polymerization reaction product (A) to the maleic acid-modified polyolefin resin (B) is in the range of 80:20 to 20:80. 3. The method according to claim 1 or 2,
The saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2)
The polyvalent carboxylic acid residue (a1) contains a polyvalent carboxylic acid residue (a11) having three or more valences,
The amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is in the range of 1 to 50 mol%. The method of claim 3,
The polyvalent carboxylic acid residue (a1) contains an alicyclic polycarboxylic acid residue (a10)
The amount of the alicyclic polycarboxylic acid residue (a10) relative to the polyvalent carboxylic acid residue (a1) is in the range of 30 to 99 mol%. The method of claim 3,
Wherein the glycol residue (a2) contains an alicyclic glycol residue (a20)
Wherein the amount of the alicyclic glycol moiety (a20) relative to the glycol moiety (a2) is in the range of 30 to 100 mol%. 3. The method according to claim 1 or 2,
Wherein the mass ratio of the saturated polyester resin (a) and the ethylenically unsaturated monomer (b) is in the range of 99: 1 to 10: 90. 3. The method according to claim 1 or 2,
The nonionic ethylenically unsaturated monomer (b1) contains a monomer (b0) having a hydroxyl group,
Wherein the amount of the hydroxyl group-containing monomer (b0) relative to the ethylenically unsaturated monomer (b) is in the range of 1 to 40 mol%. CLAIMS What is claimed is: 1. A light emitting device comprising a substrate and a primer layer on the substrate,
Wherein the primer layer contains a dried product of the primer composition according to any one of claims 1 to 3. 9. The method of claim 8,
And an outer layer made of metal or resin on the primer layer. A process for producing a primer composition, which comprises a polymerization reaction product (A), a maleic acid-modified polyolefin resin (B) and water (C)
(A) by emulsion polymerization of the ethylenically unsaturated monomer (b) in a mixture containing a saturated polyester resin (a) and an ethylenically unsaturated monomer (b), and a step of polymerizing the polymerization reaction product ) And the maleic acid-modified polyolefin resin (B)
The saturated polyester resin (a) has an acid value in the range of 10 to 100 mgKOH / g,
Wherein the ethylenically unsaturated monomer (b) contains a nonionic ethylenically unsaturated monomer (b1). 11. The method of claim 10,
The saturated polyester resin (a) has a polyvalent carboxylic acid residue (a1) and a glycol residue (a2)
The polyvalent carboxylic acid residue (a1) contains a polyvalent carboxylic acid residue (a11) having three or more valences,
Wherein the amount of the polyvalent carboxylic acid residue (a11) relative to the polyvalent carboxylic acid residue (a1) is in the range of 1 to 50 mol%.

Images