JP2015067674A - Primer for footwear constituting member, footwear constituting member, and footwear - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer for a footwear constituting member, which has primer performance for a footwear constituting member and maintains adhesiveness under severe conditions, and a method for producing the same, and to provide a constituting member using the primer for a footwear constituting member, and footwear including the same.SOLUTION: Provided are a primer for footwear constituting member, comprising a chlorinated polyolefin resin (A), a polyurethane resin (B), and a medium, wherein a mass ratio (A/B) of the chlorinated polyolefin resin (A) and the polyurethane resin (B) is in a range of 95/5 to 20/80, and a method for producing the same. Also provided are a footwear constituting member using the primer for a footwear constituting member, and footwear including the same.

Description

  The present invention relates to a primer for adhering components in footwear.

  A technique for bonding a plurality of members having different chemical structures and mechanical properties is an important technique in footwear and footwear manufacturing. In particular, sports shoes that are subjected to strong stress during use are required to be firmly bonded to each other. Conventionally, as a footwear adhesion technology for developing such strong adhesion, each component is pre-greased, buffed, primer coated, etc. as necessary, and then coated with an adhesive. There is a method of bonding via the adhesive. Among these treatments, the primer coating is responsible for adhesion between the footwear component and the adhesive, and plays an important role as a footwear adhesion technique.

  On the other hand, sports shoes are constantly required to have high functionality in terms of various performances such as cushioning, weight reduction, and design. In order to respond to such needs for higher functionality, new materials are proposed daily for the components of footwear. Of course, when such a new material is used as a component of footwear, a high-level bonding technique is required. Therefore, even if such a novel material is proposed, there are cases where the conventional primer cannot be put into practical use because sufficient adhesion cannot be obtained. In other words, the new material also requires a primer corresponding to it.

  In order to adapt to such a novel material, Patent Documents 1 and 2 propose primers for footwear.

Special table 2003-521547 gazette JP 2005-290313 A

  However, even with the primers described in Patent Documents 1 and 2, there are materials that cannot be sufficiently bonded. In particular, the component constituting the sole, which is called the sole, is often improved in functionality such as weight reduction by using various polyolefin resins as substitutes. Because of its weak polarity, there is still no adhesion technology that can realize sufficient adhesion.

  On the other hand, footwear is used in various environments and is often used for a long time. Therefore, the adhesiveness between the respective members constituting the footwear needs to be sufficiently ensured even when used for a long time in a harsh environment. However, Patent Documents 1 and 2 do not describe any adhesiveness or primer effect retention under environmental conditions.

  The present invention eliminates the disadvantages of the prior art as described above, and maintains good adhesion even when a polyolefin resin is used as a component of footwear or even in harsh usage environments. It is an object of the present invention to provide a primer for footwear constituent members.

  As a result of intensive studies to solve the above problems, the present inventors have found that a primer containing a chlorinated polyolefin resin and a polyurethane resin in a specific quantitative ratio solves the above problems, and reached the present invention. did.

  That is, the gist of the present invention is as follows.

(1) A chlorinated polyolefin resin (A), a polyurethane resin (B), and a medium are contained, and the mass ratio (A / B) of the chlorinated polyolefin resin (A) and the polyurethane resin (B) is 95/5. The primer for footwear constituent members characterized by being in the range of ~ 20/80.
(2) The chlorinated polyolefin resin (A) contains an unsaturated carboxylic acid component, and the acid value of the chlorinated polyolefin resin (A) is in the range of 1 to 100 mgKOH / g. Primer for footwear components.
(3) An aqueous dispersion in which the medium is an aqueous medium, the chlorinated polyolefin resin (A) and the polyurethane resin (B) are dispersed in the aqueous medium, and the chlorinated polyolefin resin (A) and the polyurethane resin (B). The primer for footwear constituent members according to (1) or (2), wherein the number average particle diameter of the dispersed particles is 1 μm or less.
(4) The primer for footwear constituent members according to claims 1 to 3, wherein the chlorinated polyolefin resin (A) contains 20% by mass or more of a propylene unit as an olefin component.
(5) The primer for footwear constituent members according to any one of claims 1 to 4, which is applied to a footwear constituent member made of a polyolefin-based resin.
(6) A footwear constituent member, wherein a primer layer obtained from the primer for footwear constituent member according to any one of (1) to (5) is laminated on at least a part of the surface.
(7) A footwear comprising the footwear constituent member according to (6).
(8) A footwear comprising the footwear constituent member according to (6) bonded to the footwear by a polyurethane adhesive provided through a primer layer.

  The primer for footwear constituent member of the present invention has excellent adhesiveness to footwear constituent members, particularly footwear constituent members made of polyolefin resin, and is provided via a primer layer obtained from the footwear constituent member primer. With the adhesive thus formed, it becomes possible to firmly combine (adhere) the footwear component in the footwear. Furthermore, the adhesiveness is sufficiently ensured even when used for a long time in a harsh environment.

  The present invention will be described in detail below.

  First, the chlorinated polyolefin resin (A) will be described. As the polyolefin resin that is a raw material of the chlorinated polyolefin resin (A) in the present invention, a crystalline polypropylene resin, an amorphous polypropylene resin, a crystalline polyethylene resin, an amorphous polyethylene resin, an ethylene-α-olefin copolymer, A propylene-α-olefin copolymer, an ethylene-vinyl acetate copolymer and the like can be mentioned, and a mixture thereof can also be used. As the olefin component, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, 1-octene and the like have 2 or more carbon atoms, preferably carbon The alkene of several 2-6 is mentioned, These mixtures can also be used. Among them, it is preferable that the propylene unit is contained in an amount of 20% by mass or more from the viewpoint of adhesiveness with the polyolefin resin member, more preferably 40% by mass or more, particularly preferably 50% by mass or more, and further preferably 60% by mass or more. 70% by mass or more is most preferable.

The chlorinated polyolefin resin (A) in the present invention preferably contains an unsaturated carboxylic acid component from the viewpoint of adhesiveness and aqueous dispersion described later. Examples of the unsaturated carboxylic acid component include acrylic acid, methacrylic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, and crotonic acid. Other examples include half esters and half amides of unsaturated dicarboxylic acids. Among these, acrylic acid, methacrylic acid, and (anhydrous) maleic acid are preferable from the viewpoint of adhesion and ease of copolymerization, and (anhydrous) maleic acid is particularly preferable. Moreover, the unsaturated carboxylic acid component should just be copolymerized in the chlorinated polyolefin resin, and the form is not limited. Examples of the state of copolymerization include random copolymerization, block copolymerization, and graft copolymerization (graft modification).
In addition, “(anhydrous) to acid” means “to acid or anhydrous to acid”. That is, (anhydrous) maleic acid means maleic acid or maleic anhydride.

  The acid value of the chlorinated polyolefin resin (A) serving as an index of the content of the unsaturated carboxylic acid component is preferably in the range of 1 to 100 mgKOH / g, more preferably 5 to 50 mgKOH / g, and 10 to 40 mgKOH / g. g is particularly preferable, and 20 to 40 mg KOH / g is more preferable. Adhesiveness and aqueous dispersion can be made favorable when the acid value is in the preferred range.

  As a method of chlorinating polyolefin resin, after dissolving the resin to be chlorinated in a chlorinated solvent such as chloroform, irradiation with ultraviolet rays or radical generators such as organic peroxides and azonitriles It can be carried out by blowing gaseous chlorine in the presence. Chlorination may be performed before or after introducing the unsaturated carboxylic acid unit described above. That is, there are a method in which an unsaturated carboxylic acid unit is introduced into a polyolefin resin and then chlorinated, and a method in which an unsaturated carboxylic acid unit is introduced after chlorinating a polyolefin resin. In addition, chlorination means what substituted some hydrogen atoms in polyolefin resin with chlorine.

  The chlorine content in the chlorinated polyolefin resin (A) is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass, and further preferably 10 to 40% by mass. 10 to 35% by mass is most preferable. When the chlorine content is less than 3% by mass, the effect of chlorination is small, and when it exceeds 70% by mass, the adhesion to the polyolefin resin member tends to be reduced.

  The chlorinated polyolefin resin (A) in the present invention may contain components other than those described above as necessary. Other components include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, maleic acid such as dimethyl maleate, diethyl maleate, and dibutyl maleate. Acid esters, (meth) acrylic amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and vinyl esters Vinyl alcohol, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, vinyl halides, vinylidene halides, carbon monoxide, two Sulfur, and the like, may be a mixture thereof. The other component should just be copolymerized in the chlorinated polyolefin resin, and the form is not limited. Examples of the state of copolymerization include random copolymerization, block copolymerization, and graft copolymerization (graft modification). Moreover, as content (mass ratio) of another component, 10 mass% or less of the whole chlorinated polyolefin resin (A) is preferable.

  The weight average molecular weight of the chlorinated polyolefin resin (A) is preferably from 5,000 to 300,000, more preferably from 10,000 to 200,000, and preferably from 20,000 to 150,000. Particularly preferred is 30,000 to 100,000. When the weight average molecular weight is out of the preferred range, the adhesion with the polyolefin resin member tends to be lowered. In addition, the weight average molecular weight of resin can be calculated | required on the basis of polystyrene resin using a gel permeation chromatography (GPC).

  Next, the polyurethane resin (B) will be described. The polyurethane resin (B) in the present invention is a polymer containing a urethane bond in the main chain, and is obtained, for example, by a reaction between a polyol compound and a polyisocyanate compound.

  The polyurethane resin (B) in the present invention preferably has an anionic group from the viewpoint of adhesiveness and dispersibility in an aqueous medium. An anionic group is a functional group that becomes an anion in an aqueous medium, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group. Among these, it is preferable to have a carboxyl group.

  The polyol component constituting the polyurethane resin is not particularly limited. For example, water, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1 , 3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexane Low molecular weight glycols such as diol, diethylene glycol, triethylene glycol, and dipropylene glycol; low molecular weight polyols such as trimethylolpropane, glycerin, and pentaerythritol; and polyols having ethylene oxide and propylene oxide units. Le compounds, polyether diols, high molecular weight diols such as polyester diols, bisphenols such as bisphenol A, bisphenol F, dimer diol, and the like to the carboxyl group of the dimer acid was converted to hydroxyl groups.

  Further, as the polyisocyanate component, one or a mixture of two or more known aromatic, aliphatic and alicyclic known diisocyanates can be used. Specific examples of the diisocyanates include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, Examples thereof include lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and adducts, biurets, and isocyanurates. As the diisocyanate, trifunctional or higher functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate may be used. Of these, isophorone diisocyanate is preferred as the isocyanate component from the viewpoint of improving adhesiveness.

  In order to introduce an anionic group into the polyurethane resin, a polyol component having a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group or the like may be used. As a polyol compound having a carboxyl group, 3,5 -Dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis ( 4-hydroxyphenyl) acetic acid, 2,2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxyl-propionamide, etc. Is mentioned.

  Further, the molecular weight of the polyurethane resin can be appropriately adjusted using a chain extender. Examples of such compounds include compounds having two or more active hydrogens such as amino groups and hydroxyl groups capable of reacting with isocyanate groups. For example, diamine compounds, dihydrazide compounds, and glycols can be used.

  Examples of the diamine compound include ethylenediamine, propylenediamine, hexamethylenediamine, triethyltetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and the like. Other examples include diamines having a hydroxyl group such as N-2-hydroxyethylethylenediamine and N-3-hydroxypropylethylenediamine, and dimer diamine obtained by converting the carboxyl group of dimer acid into an amino group. Furthermore, diamine type amino acids such as glutamic acid, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid and diaminobenzenesulfonic acid are also included.

  Dihydrazide compounds include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacin dihydrazide, etc., saturated aliphatic dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, etc. And unsaturated dihydrazides such as itaconic acid dihydrazide and phthalic acid dihydrazide, carbonic acid dihydrazide, carbodihydrazide, and thiocarbodihydrazide.

  As glycols, they can be appropriately selected from the aforementioned polyols.

  The polyurethane resin (B) in the present invention is preferably a polycarbonate-type polyurethane resin, a polyether-type polyurethane resin or a polyester-type polyurethane resin from the viewpoint of adhesion, and from the viewpoint of adhesion retention in a harsh environment, the polycarbonate-type polyurethane. A resin and a polyether type polyurethane resin are more preferable, and a polyether type polyurethane resin is particularly preferable.

  In addition, although the polyurethane resin (B) in this invention is utilized as a coating agent disperse | distributed and / or melt | dissolved in the medium mentioned later, a polyurethane resin (B) is any of 2 liquid type and 1 liquid type. It does not matter. However, the one-pack type is preferable from the viewpoint of long pot life and excellent workability during use. Here, from the viewpoint of pot life, the two-component type polyurethane resin includes a main agent mainly composed of a polyol component and a curing agent mainly composed of an isocyanate component immediately before use (up to about 12 hours before use). It is a polyurethane resin used after mixing, and is a type in which the polyol component in the main agent and the isocyanate component in the curing agent react to form a film as the medium evaporates. The one-component type polyurethane resin is a polyurethane resin that has a long pot life and does not require mixing of a plurality of components immediately before use, and is a type that forms a film even only by evaporation of a medium. .

  In the present invention, the mass ratio (A / B) of the chlorinated polyolefin resin (A) and the polyurethane resin (B) needs to be in the range of 95/5 to 20/80, and in the range of 70/30 to 40/60. Is preferable, and the range of 60/40 to 45/55 is more preferable. When (A / B) is within the range specified by the present invention, the primer for footwear constituent members of the present invention has good adhesion and excellent adhesion retention under the environment.

  The primer for footwear members of the present invention contains a chlorinated polyolefin resin (A), a polyurethane resin (B), and a medium, and includes chlorinated polyolefin resin (A) and polyurethane resin ( B) is a coating agent formed by dispersing and / or dissolving in a medium. Examples of the medium include an organic solvent or an aqueous medium. The aqueous medium is water or a liquid containing water as a main component, and may contain a basic compound or an organic solvent described later.

  When an organic solvent is used as the medium, it is preferable to select an organic solvent in which the chlorinated polyolefin resin (A) and the polyurethane resin (B) can be dissolved. In such a case, the chlorinated polyolefin resin (A) and A solution containing the polyurethane resin (B) is preferably used as a primer for footwear members from the viewpoint of ease of coating. Specific examples of the organic solvent include halogen-based organic solvents such as perchloroethylene, trichloroethylene, methylene chloride, and chloroform; hydrocarbon compounds such as hexane, heptane, and pentane; aromatic compounds such as benzene, toluene, and xylene; ethanol, 1 Alcohol compounds such as propanol, 2-propanol, 1-butanol and 2-butanol; ether compounds such as diethyl ether, tetrahydrofuran and t-butyl methyl ether; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl formate; Non-halogen organic solvents such as ester compounds such as methyl acetate, ethyl acetate, propyl acetate, and isopropyl acetate; These may be used in combination. Of these, hydrocarbon compounds, aromatic compounds, ketone compounds, and ester compounds are preferred from the viewpoint of solubility of the chlorinated polyolefin resin (A) and the polyurethane resin (B). In addition, although the primer for footwear members using an organic solvent as a medium does not need to intentionally use water as a raw material, it does not exclude the inclusion of water. A trace amount of water may be contained depending on the use of the material that has absorbed water. The water content is preferably 1% by mass or less of the entire primer for footwear members, and 0.5% by mass or less. More preferred is 0.2% by mass or less.

  As a method of dissolving the chlorinated polyolefin resin (A) and the polyurethane resin (B) in an organic solvent, a known method can be adopted. For example, the chlorinated polyolefin resin (A) and the polyurethane resin (B ), Stirring, and heating if necessary. (A) and (B) may be dissolved separately and then mixed together. The solution containing the chlorinated polyolefin resin (A) and the polyurethane resin (B) is preferably prepared in a uniform liquid state.

  When an aqueous medium is used as the medium, the aqueous solution containing the chlorinated polyolefin resin (A) and the polyurethane resin (B) in which both the chlorinated polyolefin resin (A) and the polyurethane resin (B) are dispersed in the aqueous medium. It is preferable that the dispersion is used as a primer for footwear members because of easy coating. The aqueous dispersion containing the chlorinated polyolefin resin (A) and the polyurethane resin (B) is preferably prepared in a uniform liquid state.

  Here, the term “uniform liquid state” means that a portion where the solid content concentration is locally different from other portions such as precipitation, phase separation or skinning is not found in the solution and / or the aqueous dispersion. It means being in a state.

  Next, the manufacturing method of the aqueous dispersion in this invention is demonstrated.

  As a method of dispersing the chlorinated polyolefin resin (A) and the polyurethane resin (B) in the aqueous medium, for example, the chlorinated polyolefin resin (A) and the polyurethane resin (B) are separately dispersed in the aqueous medium, and then both And a method in which the chlorinated polyolefin resin (A) and the polyurethane resin (B) are charged into a dispersion apparatus and dispersed in an aqueous medium. Among them, a method in which the chlorinated polyolefin resin (A) and the polyurethane resin (B) are individually dispersed in an aqueous medium and then mixed together is preferable because it is easy to produce.

  As a method of dispersing the chlorinated polyolefin resin (A) in an aqueous medium, a known method can be employed. Specifically, a method of heating and stirring a chlorinated polyolefin resin (A) and an aqueous medium (such as an organic solvent and a basic compound as necessary) in a sealable container can be employed. By using such a method, the chlorinated polyolefin resin (A) can be processed into an aqueous dispersion without substantially using a non-volatile aqueous dispersion aid described later.

  As a method of dispersing the polyurethane resin (B) in an aqueous medium, a known method can be adopted. Among them, it is preferable to adopt a method that enables dispersion without substantially using a non-volatile aqueous dispersion aid.

  The aqueous dispersion of the chlorinated polyolefin resin (A) and the aqueous dispersion of the polyurethane resin (B) obtained individually as described above are the chlorinated polyolefin resin (A) and the polyurethane resin (B ) Mass ratio (A / B) so as to be within the range specified in the present invention, it is possible to obtain the footwear component primer of the present invention. The mixing method is not particularly limited as long as the aqueous dispersion of the chlorinated polyolefin resin (A) and the aqueous dispersion of the polyurethane resin (B) are uniformly mixed. The aqueous dispersion of the polyurethane resin (B) may be added to the aqueous dispersion of the chlorinated polyolefin resin (A), or the aqueous dispersion of the polyurethane resin (B) may be added to the aqueous dispersion of the chlorinated polyolefin resin (A). An aqueous dispersion of may be added. After mixing both, it may stir to homogenize, or the other aqueous dispersion may be added and mixed while stirring. The temperature of the aqueous dispersion at the time of mixing is usually no problem at ordinary temperature, but a heated aqueous dispersion may be mixed as necessary.

  Next, the aqueous dispersion containing the chlorinated polyolefin resin (A) and the polyurethane resin (B) will be described.

  The number average particle diameter of the dispersed particles composed of the chlorinated polyolefin resin (A) and the polyurethane resin (B) dispersed in the aqueous dispersion in the present invention is preferably 1 μm or less, 0.01 to 0 The range of 0.5 μm is more preferable, the range of 0.03 to 0.4 μm is particularly preferable, the range of 0.05 to 0.3 μm is further preferable, and the range of 0.1 to 0.2 μm is most preferable. When the number average particle diameter exceeds 1 μm, the adhesion and the adhesion retention under the environment tend to be lowered. The dispersed particle size can be increased by adding an acidic compound to the aqueous dispersion.

  In the present invention, the content of nonvolatile components including the chlorinated polyolefin resin (A) and the polyurethane resin (B) contained in the aqueous dispersion can be appropriately selected according to the coating conditions, coating thickness, performance, etc. Although not limited, 1-60 mass% is preferable, 3-55 mass% is more preferable, and 5-50 mass% is preferable at the point which maintains the viscosity of an aqueous dispersion moderately and expresses favorable coating property. Is more preferable, and 10 to 45% by mass is particularly preferable.

  The aqueous dispersion in the present invention preferably contains substantially no nonvolatile aqueous dispersion aid. The present invention does not exclude the use of a non-volatile aqueous dispersion aid, but without using an aqueous dispersion aid, the dispersed particles can be stably dispersed in an aqueous medium within the range of a number average particle diameter of 1 μm or less. Can be dispersed. Since the aqueous dispersion in the present invention does not substantially contain a non-volatile aqueous dispersion aid, it is excellent in primer properties, in particular, adhesion to footwear components and water resistance.

  Here, the “aqueous dispersion aid” is a drug or compound added for the purpose of promoting aqueous dispersion or stabilizing the aqueous dispersion in the production of the aqueous dispersion. Means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure.

  “Substantially no non-volatile aqueous dispersion aid” is obtained without using such an aid during production (when chlorinated polyolefin resin (A) and polyurethane resin (B) are dispersed in water). It means that the aqueous dispersion does not contain this auxiliary as a result. Therefore, the content of such an aqueous dispersion aid is particularly preferably zero. However, the total of the chlorinated polyolefin resin (A) and the polyurethane resin (B) (A + B) within a range not impairing the effects of the present invention. 5 mass% or less, preferably 2 mass% or less, and more preferably less than 0.5 mass% may be contained.

  Examples of the non-volatile aqueous dispersion aid used in the present invention include an emulsifier described later, a compound having a protective colloid effect, a modified wax, a high acid value acid-modified compound, a water-soluble polymer, and the like.

  Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

  Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polyvinylpyrrolidone , Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, and other acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydride Maleic acid copolymer and its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as a copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, and a salt thereof, polyitaconic acid and a salt thereof, and an amino group. Examples thereof include water-soluble acrylic copolymers, gelatin, gum arabic, casein, and the like compounds generally used as fine particle dispersion stabilizers.

  The aqueous medium contained in the aqueous dispersion in the present invention is water or a liquid containing water as a main component. The content of water in the aqueous medium is preferably 10 to 100% by mass of the entire aqueous medium from the viewpoint of dispersion stabilization, more preferably 20 to 100% by mass, particularly preferably 30 to 100% by mass, and 40 to 40%. 100 mass% is more preferable, and 50-100 mass% is the most preferable.

  The aqueous medium in the aqueous dispersion in the present invention preferably contains a basic compound in addition to water. Aggregation between fine particles is prevented by the electric repulsion between the carboxyl anions generated by neutralizing the carboxyl groups contained in the chlorinated polyolefin resin (A) and polyurethane resin (B) contained in the aqueous dispersion with a basic compound. The stability is imparted to the aqueous dispersion. The basic compound is not particularly limited as long as it can neutralize the carboxyl group, but from the viewpoint of primer properties, it is preferable to use a volatile compound.

  As the basic compound, ammonia and organic amines are preferable. Specific examples of the organic amine include triethylamine, N, N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, and 3-diethylamino. Propylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrrole, Examples thereof include pyridine. It is preferable that the compounding quantity of a basic compound is 0.5-10 times equivalent with respect to the carboxyl group in a chlorinated polyolefin resin (A) and a polyurethane resin (B), and 0.8-5 times equivalent is more. 0.9 to 3.0 times equivalent is particularly preferable. If the amount is less than 0.5 times equivalent, the effect of adding a basic compound is not observed, and if the amount exceeds 10 times equivalent, the drying time during the formation of the primer layer may be prolonged, or the stability of the aqueous dispersion may be lowered.

  Furthermore, the aqueous medium in the aqueous dispersion in the present invention may contain an organic solvent. The wettability to the footwear component can be improved by containing an organic solvent. Furthermore, by adding at the time of aqueous dispersion of the chlorinated polyolefin resin (A), it has the effect of promoting aqueous dispersion and reducing the dispersed particle size. As content of the organic solvent in an aqueous dispersion, 80 mass% or less is preferable with respect to the whole aqueous dispersion, it is more preferable that it is 0.1-60 mass%, and 1-50 mass% is especially preferable. When the content of the organic solvent exceeds 80% by mass, the stability of the aqueous dispersion may be lowered.

  The organic solvent preferably has a solubility in water at 20 ° C. of 10 g / L or more, more preferably 20 g / L or more, and 50 g / L or more from the viewpoint of aqueous dispersion promotion performance and dispersion stability. Particularly preferred. Moreover, the thing whose boiling point is 200 degrees C or less is preferable from a dry viewpoint at the time of drying a footwear structural member primer and obtaining a primer layer. An organic solvent having a boiling point exceeding 200 ° C. tends to remain in the primer layer, and in particular, the water resistance of the primer layer during low-temperature drying and adhesion to footwear components may be deteriorated. Preferred organic solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol. , Alcohols such as 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane , Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate , Esters such as ethyl propionate, diethyl carbonate, dimethyl carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, glycol derivatives such as ethylene glycol ethyl ether acetate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1,2 -Dimethyl glycerol, 1, 3- dimethyl glycerol, a trimethyl glycerol, etc. are mentioned. In the present invention, a mixture of these organic solvents may be used.

  Among the above organic solvents, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether are chlorinated. It is effective and effective in promoting aqueous dispersion of the polyolefin resin (A).

  As described above, the organic solvent is preferably added at the time of aqueous dispersion in order to promote aqueous dispersion. However, after aqueous dispersion, the wettability, stability, and solid content of the organic solvent are increased. Some or all of them may be removed by a method such as stripping, which will be described later, in consideration of adjustment and the like.

  Although the viscosity measured in 20 degreeC conditions with the B-type viscometer of the aqueous dispersion in this invention is not specifically limited, It can use preferably in the range of 4-100,000 mPa * S. The aqueous dispersion pH is not particularly limited, but can be preferably used in the range of pH 6-12.

  The primer for footwear constituent members of the present invention is a chlorinated polyolefin resin (A) using an aqueous medium as described above from a solution containing a chlorinated polyolefin resin (A) and a polyurethane resin (B) using an organic solvent. And the aqueous dispersion containing the polyurethane resin (B) is preferable from the viewpoint of adhesiveness and adhesion retention under the environment. Furthermore, an aqueous dispersion is preferable from the viewpoint of environmental protection and health maintenance of footwear manufacturing workers.

  The primer for footwear component of the present invention is referred to as a resin other than the chlorinated polyolefin resin (A) and the polyurethane resin (B) (hereinafter referred to as “other resin”) in order to further improve the performance depending on the purpose. There may be added tackifiers, crosslinking agents, inorganic particles, pigments, dyes, and the like.

  Other resins and tackifiers are not particularly limited. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, styrene -Adhesives such as maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, polyester resin, polyacrylic resin, modified nylon resin, rosin or terpene Examples include an imparting resin, a phenol resin, a silicone resin, and an epoxy resin, and a plurality of them may be mixed and used as necessary.

  As the crosslinking agent, a crosslinking agent having self-crosslinking property, a crosslinking agent having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, and the like can be used. Specifically, an oxazoline crosslinking agent, an isocyanate crosslinking agent (including a block type), an amine crosslinking agent, a carbodiimide crosslinking agent, a melamine crosslinking agent, a urea crosslinking agent, an epoxy crosslinking agent, a zirconium salt compound, Examples include silane coupling agents and organic peroxides, and these crosslinking agents may be used in combination. The crosslinking agent may be a low molecular weight compound or a polymer type.

  Among these, a crosslinking agent having a plurality of functional groups that react with carboxyl groups in the molecule is more preferable. Examples of such crosslinking agents include oxazoline-based crosslinking agents, epoxy-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, amine-based crosslinking agents, and melamine-based crosslinking agents. A cross-linking agent, an amine-based cross-linking agent, and a carbodiimide-based cross-linking agent are preferable because an adhesive improvement effect and cold adhesiveness are maintained, and an isocyanate-based cross-linking agent and an amine compound are particularly preferable.

  The addition amount of the crosslinking agent is 0 with respect to 100 parts by mass of the total (A + B) of the chlorinated polyolefin resin (A) and the polyurethane resin (B) contained in the primer for footwear component from the viewpoint of sufficiently forming a crosslinked structure. 0.1-30 parts by mass is preferable, 0.2-20 parts by mass is more preferable, and 0.5-15 parts by mass is even more preferable.

  Examples of inorganic particles include metal oxides such as magnesium oxide, zinc oxide and tin oxide, inorganic particles such as calcium carbonate and silica, and layered inorganic compounds such as vermiculite, montmorillonite, hectorite, hydrotalcite and synthetic mica. Can be used. The average particle diameter of these inorganic particles is preferably 0.005 to 10 μm, more preferably 0.005 to 5 μm from the viewpoint of the stability of the aqueous dispersion. In addition, a plurality of inorganic particles may be mixed and used. Here, zinc oxide can be used for ultraviolet shielding, and tin oxide can be used for antistatic purposes.

  Examples of pigments and dyes include titanium oxide, zinc white, and carbon black, and any of disperse dyes, acid dyes, cationic dyes, reactive dyes, and the like can be used. If necessary, various agents such as a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersant, an ultraviolet absorber, a thickener, a weathering agent, a flame retardant are added to the aqueous dispersion of the present invention. It is also possible. These may be used alone or in combination of two or more.

  Next, the usage method of the primer for footwear components of this invention is demonstrated.

  The primer for footwear component of the present invention can be coated on the footwear component by a known method, for example, brush coating, brush coating, knife coating, spray coating, dip coating, lip coating, curtain flow coating. Gravure roll coating, reverse roll coating, wire bar coating, etc. can be employed, and among these, brush coating, brush coating, etc. suitable for the production of footwear can be preferably applied.

  Specifically, the primer for the footwear constituent member is made as uniform as possible on the entire surface of the footwear constituent member or part of the surface of the footwear constituent member, which has been subjected to a known pretreatment such as degreasing and buffing as necessary. The primer layer is laminated on the footwear component by coating the thickness and setting it near room temperature as necessary, followed by drying to volatilize part or all of the media contained in the footwear component primer. Is possible. After drying, various treatments such as baking may be performed as necessary. As a heating device at the time of drying or baking, a known device such as a normal hot air dryer or an infrared heater can be used. The heating temperature and heating time for drying are appropriately determined depending on the characteristics of footwear constituent members that are to be coated, the characteristics of various materials such as the above-mentioned crosslinking agents that can be optionally mixed in the primer for footwear constituent members, and the degree of addition. The heating temperature is preferably 30 to 150 ° C, more preferably 40 to 100 ° C, and particularly preferably 50 to 80 ° C. The heating time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes, and particularly preferably 5 to 20 minutes.

As the coating amount of the footwear component primer for footwear components of the present invention, preferably 0.1~300g / ^{m 2} as a primer layer after drying, more preferably 1-200 g / ^{m 2,.} 5 to particularly preferably 100 g / ^{m 2,} further preferably 10 to 80 g / ^{m 2.} When the coating amount is out of the above range, the effect as a primer tends to decrease. In order to adjust the coating amount, it is preferable to use a primer for footwear components whose concentration is adjusted according to the target coating amount, in addition to appropriately selecting a coating method and its conditions. The concentration at this time can be adjusted by the charged composition at the time of preparation. Further, once prepared, the primer for footwear component may be adjusted by appropriately diluting or concentrating by a method such as stripping.

  As described above, a footwear constituent member in which a primer layer obtained from the footwear constituent member primer is laminated on at least a part of the surface can be obtained.

  Next, a method of using the footwear constituent member on which the primer layer is laminated with another footwear constituent member (the other adherend to be bonded to the footwear constituent member, hereinafter also referred to as “partner material”) Will be described. In addition, it is preferable to perform surface treatment such as degreasing, buffing, primer coating, and the like suitable for the material when bonding the counterpart material. Moreover, as long as the material of the counterpart material is suitable for the primer for footwear constituent members of the present invention, the primer for footwear constituent members of the present invention may be coated as a primer for surface treatment.

  In the present invention, an adhesive is coated on the primer layer on the surface of the footwear component (that is, the adhesive is coated via the primer layer) and dried to form an adhesive layer. The adhesive strength of the adhesive layer Can be bonded to the mating material. As the adhesive used, known footwear adhesives such as polyurethane adhesives and chloroprene adhesives can be used, and these may be solvent-based or water-based. Among them, it is preferable to use a polyurethane adhesive because it has more excellent adhesiveness. The polyurethane adhesive may be either a one-component type or a two-component curable type, but a two-component curable type is more preferable from the viewpoint of adhesiveness. From the viewpoint of pot life, a two-component curable polyurethane adhesive is composed of a main component mainly composed of a polyol component and a curing agent mainly composed of an isocyanate component immediately before use (up to about 12 hours before use). It is a polyurethane adhesive used after mixing, and is a type in which the polyol component in the main agent reacts with the isocyanate component in the curing agent together with the evaporation of the medium containing the adhesive.

A known method can be adopted as a method of using these adhesives. For example, a polyurethane adhesive is applied to the surface of the footwear component of the present invention provided with a primer layer, and the amount of the adhesive layer after drying is preferably in the range of ^{20 to} 200 g / m ² , more preferably 50 to 150 g. / M ² is coated with a brush so that the surface of the mating material is coated with the same adhesive. Next, as drying conditions, the drying temperature is preferably in the range of 40 to 100 ° C., more preferably in the range of 50 to 80 ° C., the drying time is preferably in the range of 1 to 30 minutes, and more preferably in the range of 10 to 20 minutes. The adhesive coated on the footwear component and the counterpart material is dried to form an adhesive layer, and then the temperature of the adhesive layer heated by drying is preferably maintained at 30 ° C or higher, more preferably 40 ° C or higher. In this state, there is a method in which the footwear constituent member and the adhesive layer provided on the counterpart material are bonded to each other, and the footwear constituent member and the counterpart material are preferably pressure-bonded with a high pressure within a range in which the footwear constituent member and the counterpart material do not deform.

  The footwear including the footwear constituent member of the present invention can be obtained by further processing the footwear constituent member and the counterpart material bonded to the footwear as described above. That is, the footwear component of the present invention can be bonded to the footwear.

  Although it does not specifically limit as a footwear component applicable to the primer for footwear components of this invention, It is mainly sole (shoe sole) parts, such as an outer sole, a midsole, an insole, the shock absorbing material provided in the sole, and a shank. It is suitably used for the constituent members. In addition, as a material of the footwear constituent member, any material can be used as long as the adhesive strength between the footwear constituent member bonded with the footwear constituent member primer and the counterpart material exhibits good adhesion such as 20 N / 20 mm or more. Although not particularly limited, from the viewpoint of adhesiveness, it is preferably made of a polyolefin resin, and more preferably made of a polypropylene resin. The material comprising a polyolefin-based resin in the present invention means a material containing at least a polyolefin resin or a polyolefin copolymer as a constituent material, and these may be a polyolefin resin or a polyolefin copolymer alone, or other than these These resins and components may be blended. The material composed of a polypropylene resin means a material containing at least a polypropylene resin or a polypropylene copolymer as a constituent material, which may be a polypropylene resin or a polypropylene copolymer alone, The components may be blended.

  The footwear of the present invention obtained by the above-described adhesion method using the primer for footwear constituent member of the present invention is excellent in adhesion between the footwear constituent member and the counterpart material. The strength (adhesion strength) required to peel off the footwear component and the counterpart material bonded via the primer layer and the adhesive layer is strong or weak depending on the function, material, shape, etc. of the footwear component, Usually, when measured using a test piece cut to a width of 20 mm, it is preferably 20 N / 20 mm or more, more preferably 30 N / 20 mm or more, particularly preferably 40 N / 20 mm or more, and 60 N / 20 mm or more is more preferable, and it is most preferable that the footwear component breaks during measurement.

  Further, the footwear constituent member and the counterpart material bonded through the primer for footwear constituent member and the adhesive layer of the present invention can maintain good adhesiveness even when used for a long time in a harsh environment. The adhesiveness is preferably 20 N / 20 mm or more, more preferably 30 N / 20 mm or more, and more preferably 40 N / 20 mm or more when measured using a test piece cut to a width of 20 mm as described above. Is particularly preferably 60 N / 20 mm or more, and most preferably destruction of the footwear component occurs during measurement.

  A primer capable of adhering the footwear component or the material constituting it with the above strength is recognized as being suitable as a primer for footwear components.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Various characteristics were measured or evaluated by the following methods.

1. Characteristics of Chlorinated Polyolefin Resin (A) (1) Chlorine Content Chlorine content was determined according to the following formula according to JISK7229.
Chlorine content (% by mass) = {(A−B) × F} / S × 100
A: Amount of 0.0282N silver nitrate aqueous solution required for titration of sample (ml)
B: Amount of 0.0282N silver nitrate aqueous solution required for titration of empty sample (ml)
F: Titer of 0.0282N silver nitrate aqueous solution S: Mass of sample (mg)
(2) Acid value It measured according to JISK5407 and calculated | required the acid value (mgKOH / g).
(3) Weight average molecular weight The weight average molecular weight was determined by GPC analysis (using a liquid feeding unit LC-10Advp type and UV-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation, in terms of polystyrene).

2. Characteristics of aqueous dispersion (1) Number average particle diameter of dispersed particles comprising chlorinated polyolefin resin (A) and polyurethane resin (B) Nikkiso Co., Ltd., Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) The number average particle size was measured. The refractive index of the resin was 1.5.

3. Primer performance (1) Adhesiveness A test piece in which various materials that can become footwear constituent members are bonded together by the following methods a to e, and then a tensile tester (manufactured by Intesco, Intesco precision universal material testing machine) 2020) was used to measure the strength required to peel the footwear constituent member and the mating material in the test piece under the conditions of a tensile rate of 50 mm / min, 180 ° peeling, and 25 ° C. Measurement was performed at n = 5, and the average value was defined as adhesiveness.

  Note that rubber and EVA (ethylene / vinyl acetate copolymer) used in the methods a to e are materials generally used as footwear components such as an outer sole and a mitt sole of footwear.

a. Preparation of polypropylene resin / rubber test piece Amount of primer layer after drying on one side of a polypropylene resin (hereinafter sometimes referred to as “PP”) sheet (size: 100 mm × 50 mm × thickness 3 mm) degreased with acetone The primer for footwear constituent members was coated with a brush so that the weight became 50 g / m ² and dried at 60 ° C. for 20 minutes with a hot air dryer to obtain a footwear constituent member having a primer layer laminated thereon. Next, as a counterpart material, a rubber sheet made of styrene / butadiene rubber (size 100 mm × 50 mm × 2 mm, buffed on one side and a rubber primer on the buffing surface (N-Tape Industries P-740, polyurethane primer, EVA primer) (Hereinafter also referred to as “SBR sheet”), and a solvent-based two-component curable polyurethane adhesive (on the primer layer surface of the footwear component and the primer surface of the counterpart material) DB-1900 manufactured by Diabond Kogyo Co., Ltd. as the liquid containing the polyol compound, and Dismodule RE manufactured by Sumika Bayer Urethane Co., Ltd. as the liquid containing the polyisocyanate, and mixed at DB-1900 / Dismodule RE = 100/1. Hereinafter, this two-component curable polyurethane adhesive is referred to as “ Each of them was coated with a brush so that the amount of the adhesive layer after drying was 120 g / m ² , and then dried at 60 ° C. for 20 minutes in a hot air dryer. After drying, the adhesive layers of the footwear constituent member and the counterpart material were immediately bonded together, and the footwear constituent member and the counterpart material were pressure-bonded for 20 seconds with a press machine having a pressure of 0.1 MPa. In this way, an adhesive structure in which PP as a footwear component and rubber as a counterpart material were bonded was obtained. The adhesive structure was allowed to stand at room temperature for 24 hours, and then cut out to a width of 20 mm to obtain a test piece having a length of 20 mm × 100 mm.

  In addition, only in the case of the test piece preparation for evaluating Example 11, it replaces with PU as an adhesive agent, and is a solvent type 2 liquid-curing type chloroprene-type adhesive agent (No Tape 9360 by No Tape Industrial Co., Ltd. and Sumika Bayer Urethane Co., Ltd.). A non-tape 9360 / dismodule RE = 100/1 was used, and this two-component curable chloroprene adhesive may be referred to as “CR”).

b. Preparation of test piece of polyethylene resin / rubber The amount of the primer layer after drying is 50 g / m on one side of a polyethylene resin (hereinafter referred to as PE) sheet (size: 100 mm × 50 mm × thickness 3 mm) degreased with acetone. ^The footwear constituent member primer was coated with a brush so as to be ² and dried at 60 ° C. for 20 minutes with a hot air dryer to obtain a footwear constituent member laminated with a primer layer. Next, an SBR sheet is prepared as a counterpart material, PU is applied to the primer layer surface of the footwear component and the primer surface of the counterpart material, and the amount of the adhesive layer after drying is 120 g / m ² respectively. It was coated with a brush and then dried at 60 ° C. for 20 minutes in a hot air dryer. After drying, the adhesive layers of the footwear constituent member and the counterpart material were immediately bonded together, and the footwear constituent member and the counterpart material were pressure-bonded for 20 seconds with a press machine having a pressure of 0.1 MPa. In this way, an adhesive structure was obtained in which the footwear component PE and the counterpart rubber were bonded. The adhesive structure was allowed to stand at room temperature for 24 hours, and then cut out to a width of 20 mm to obtain a test piece having a length of 20 mm × 100 mm.

  Note that CR was used in place of PU as an adhesive only in the case of preparing a test piece for evaluating Example 11.

c. Polypropylene resin 1 / rubber test piece preparation PP pellets and styrene elastomer pellets (Clayton Polymer Japan, Clayton (registered trademark) FG1901X, maleic acid modified styrene / ethylene butylene / styrene block copolymer, hereinafter "M -SEBS ") in a mass ratio of PP / M-SEBS = 50/50 in a twin screw extruder at 220 ° C. and melt-kneaded to obtain a polypropylene resin (hereinafter referred to as“ Blend 1 ”). Pellets were obtained. The blend 1 pellets were pressed to a thickness of 3 mm with a 220 ° C. hot press to form a sheet. After processing this sheet into a 100 mm × 50 mm × 3 mm size sheet, one surface was degreased with acetone. did.

Next, the primer for footwear component is coated on the degreased surface of this Blend 1 sheet with a brush so that the amount of the primer layer after drying is 50 g / m ² and dried at 60 ° C. for 20 minutes in a hot air dryer. The footwear component having the primer layer laminated thereon was obtained. Next, an SBR sheet is prepared as a counterpart material, PU is applied to the primer layer surface of the footwear component and the primer surface of the counterpart material, and the amount of the adhesive layer after drying is 120 g / m ² respectively. It was coated with a brush and then dried at 60 ° C. for 20 minutes in a hot air dryer. After drying, the adhesive layers of the footwear constituent member and the counterpart material were immediately bonded together, and the footwear constituent member and the counterpart material were pressure-bonded for 20 seconds with a press machine having a pressure of 0.1 MPa. In this way, an adhesive structure in which the blend 1 as the footwear component and the rubber as the counterpart material were bonded was obtained. The adhesive structure was allowed to stand at room temperature for 24 hours, and then cut out to a width of 20 mm to obtain a test piece having a length of 20 mm × 100 mm.

  Note that CR was used in place of PU as an adhesive only in the case of preparing a test piece for evaluating Example 11.

d. Polypropylene resin 2 / rubber test piece preparation Propylene / 1-butene / ethylene random copolymer (mass ratio: propylene / 1-butene / ethylene = 65/25/10, hereinafter referred to as “PO”); M-SEBS is melt-kneaded at a mass ratio of PO / M-SEBS = 50/50 in a twin screw extruder at 200 ° C., and pellets of polypropylene resin (hereinafter referred to as “Blend 2”) are obtained. Obtained. This blend 2 pellet was pressed to a thickness of 3 mm with a heat press at 200 ° C. to form a sheet. After processing this sheet into a sheet of a size of 100 mm × 50 mm × 3 mm, one surface was degreased with acetone. did.

Next, the primer for footwear component is coated on the degreased surface of this blend 2 sheet with a brush so that the amount of the primer layer after drying is 50 g / m ² and dried at 60 ° C. for 20 minutes in a hot air dryer. The footwear component having the primer layer laminated thereon was obtained. Next, an SBR sheet is prepared as a counterpart material, PU is applied to the primer layer surface of the footwear component and the primer surface of the counterpart material, and the amount of the adhesive layer after drying is 120 g / m ² respectively. It was coated with a brush and then dried at 60 ° C. for 20 minutes in a hot air dryer. After drying, the adhesive layers of the footwear constituent member and the counterpart material were immediately bonded together, and the footwear constituent member and the counterpart material were pressure-bonded for 20 seconds with a press machine having a pressure of 0.1 MPa. In this way, an adhesive structure was obtained in which the blend 2 as the footwear component and the rubber as the counterpart were bonded. The adhesive structure was allowed to stand at room temperature for 24 hours, and then cut out to a width of 20 mm to obtain a test piece having a length of 20 mm × 100 mm.

  Note that CR was used in place of PU as an adhesive only in the case of preparing a test piece for evaluating Example 11.

e. Preparation of test piece of polypropylene resin / EVA Footwear composition so that the amount of the primer layer after drying is 50 g / m ² on one side of a PP molded product (size: 100 mm × 50 mm × 3 mm rectangular parallelepiped) degreased with acetone The member primer was coated with a brush and dried in a hot air dryer at 60 ° C. for 20 minutes to obtain a footwear component having a primer layer laminated thereon. Next, as a counterpart material, a foamed EVA sheet [an ethylene / vinyl acetate copolymer foam, a cube having a size of 100 mm × 50 mm × 5 mm, one surface degreased with acetone, and an EVA primer on the degreased surface (P -740, polyurethane primer, coated and dried) is prepared, and PU is applied to the primer layer surface of the footwear component and the primer surface of the counterpart material, and the amount of the adhesive layer after drying is 120 g / m ² . Each was coated with a brush and then dried at 60 ° C. for 20 minutes in a hot air dryer. After drying, the adhesive layers of the footwear constituent member and the counterpart material were immediately bonded together, and the footwear constituent member and the counterpart material were pressure-bonded for 20 seconds with a press machine having a pressure of 0.1 MPa. In this manner, an adhesive structure in which PP as a footwear component and EVA as a counterpart material were bonded was obtained. The adhesive structure was allowed to stand at room temperature for 24 hours, and then cut out to a width of 20 mm to obtain a test piece having a length of 20 mm × 100 mm.

  Note that CR was used in place of PU as an adhesive only in the case of preparing a test piece for evaluating Example 11.

(2) Adhesive retention in a harsh environment A constant temperature and humidity machine in which the test piece obtained in “d. Preparation of polypropylene resin 2 / rubber test piece” is maintained at a temperature of 65 ° C. and a humidity of 85% RH. And was taken out after 2000 hours. After taking out and leaving to stand at room temperature for 24 hours, using a tensile tester (manufactured by Intesco, Intesco precision universal material tester type 2020), the test was performed at a tensile speed of 50 mm / min, 180 ° peeling, and 25 ° C. The strength required to peel the footwear constituent member and the counterpart material in the piece was measured. The measurement was performed at n = 5, and the average value obtained was defined as adhesion retention in a harsh environment (hereinafter sometimes referred to as “adhesion retention”). The adhesion retention is closer to the adhesion value (initial value) of the test piece obtained by “d. Preparation of polypropylene resin 2 / rubber test piece” in (1) Evaluation of adhesion. It means excellent retention.

(Production of Aqueous Dispersion E-1 of Chlorinated Polyolefin Resin)
280 g of isotactic polypropylene (weight average molecular weight 70,000), 19.8 g of maleic anhydride as an unsaturated carboxylic acid, 5.6 g of dicumyl peroxide as a radical generator, and 420 g of toluene as a solvent in an autoclave equipped with a stirrer In addition, nitrogen substitution was performed for about 5 minutes, and then the reaction was performed at 140 ° C. for 5 hours with heating and stirring. After completion of the reaction, the obtained resin toluene solution was poured into a large amount of acetone to precipitate the resin. The resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer. 100 g of the obtained acid-modified polypropylene resin and 900 g of tetrachloroethylene as a solvent were added to a four-necked flask, followed by nitrogen substitution for about 5 minutes, and then heated to 110 ° C. to dissolve the resin. Next, 1.0 g of di-tert-butyl peroxide was added, and chlorine gas was blown in. After blowing 63 g of chlorine gas over 3 hours, nitrogen gas was blown to remove unreacted chlorine gas and hydrogen chloride gas. The solvent, tetrachloroethylene, was distilled off to some extent with a rotary evaporator and then dried under reduced pressure with a vacuum dryer to obtain a chlorinated polyolefin resin (chlorine content 22 mass%, acid value 27.6 mg KOH / g, weight average molecular weight 55000). . The obtained chlorinated polyolefin resin was cut into granules having a size of about 10 mm square.
Next, in a pressure-resistant 1 L glass container equipped with a stirrer capable of being sealed with a heater, 75.0 g of the chlorinated polyolefin resin, 150.0 g of tetrahydrofuran, 50.0 g of isopropanol, 15.0 g of dimethylaminoethanol, When 210.0 g of distilled water was charged and the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottom was not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 60 minutes, and then the heater was turned off and naturally cooled. When the internal temperature was lowered to 80 ° C., the pressure in the system was gradually reduced to remove tetrahydrofuran, isopropanol and water. After removing 350 g or more of tetrahydrofuran, isopropanol, and water, when the system temperature reached 35 ° C., water was added to adjust the aqueous dispersion to a chlorinated polyolefin resin concentration of 20% by mass, and 180 mesh. Was subjected to pressure filtration with a stainless steel filter to obtain an aqueous dispersion (E-1) of a milky white uniform chlorinated polyolefin resin.

(Production of aqueous dispersion E-2 of chlorinated polyolefin resin)
280 g of propylene-butene-ethylene terpolymer (manufactured by Huls Japan, Bestplast 408, propylene / butene / ethylene = 12.3 / 82.2 / 5.5% by mass) in a four-necked flask, nitrogen After being melted by heating in an atmosphere, 28.0 g of maleic anhydride as an unsaturated carboxylic acid and 5.0 g of dicumyl peroxide as a radical generator were respectively added over 2 hours while maintaining the system temperature at 170 ° C. with stirring. Thereafter, the reaction was allowed to proceed for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. The resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer. The unsaturated carboxylic acid content of this resin was 5.4% by mass. 100 g of the obtained acid-modified resin and 900 g of tetrachloroethylene as a solvent were added to a four-necked flask, followed by nitrogen substitution for about 5 minutes, and then heated to 110 ° C. to dissolve the resin. Next, 1.0 g of di-tert-butyl peroxide was added, and chlorine gas was blown in. After blowing 60 g of chlorine gas over 3 hours, nitrogen gas was blown to remove unreacted chlorine gas and hydrogen chloride gas. The solvent, tetrachloroethylene, was distilled off to some extent with a rotary evaporator and then dried under reduced pressure with a vacuum dryer to obtain a chlorinated polyolefin resin (chlorine content 18% by mass, acid value 24.7 mgKOH / g, weight average molecular weight 52000). . The obtained chlorinated polyolefin resin was cut into granules having a size of about 10 mm square.
Next, in a pressure-resistant 1 L glass container equipped with a stirrer capable of being sealed with a heater, 75.0 g of the chlorinated polyolefin resin, 150.0 g of tetrahydrofuran, 50.0 g of isopropanol, 15.0 g of dimethylaminoethanol, When 210.0 g of distilled water was charged and the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottom was not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 60 minutes, and then the heater was turned off and naturally cooled. When the internal temperature was lowered to 80 ° C., the pressure in the system was gradually reduced to remove tetrahydrofuran, isopropanol and water. After removing 350 g or more of tetrahydrofuran, isopropanol, and water, when the system temperature reached 35 ° C., water was added to adjust the aqueous dispersion to a chlorinated polyolefin resin concentration of 20% by mass, and 180 mesh. Was subjected to pressure filtration with a stainless steel filter to obtain an aqueous dispersion (E-2) of a milky white uniform chlorinated polyolefin resin.

(Production of aqueous dispersion E-3 of acid-modified polyolefin resin)
280 g of isotactic polypropylene (weight average molecular weight 50,000), 19.8 g of maleic anhydride as an unsaturated carboxylic acid, 5.6 g of dicumyl peroxide as a radical generator, and 420 g of toluene as a solvent in an autoclave equipped with a stirrer In addition, nitrogen substitution was performed for about 5 minutes, and then the reaction was performed at 150 ° C. for 5 hours with heating and stirring. After completion of the reaction, the obtained resin toluene solution was poured into a large amount of acetone to precipitate the resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride. The resin after washing with acetone was collected and dried under reduced pressure with a vacuum dryer to obtain an acid-modified polyolefin resin (chlorine content 0 mass%, acid value 32.4 mgKOH / g, weight average molecular weight 41000). The obtained acid-modified polyolefin resin was cut into granules having a size of about 10 mm square.
Next, 75.0 g of the above acid-modified polyolefin resin, 150.0 g of tetrahydrofuran, 15.0 g of dimethylaminoethanol, and 260.0 g of distilled water were placed in a 1 L pressure-resistant glass container equipped with a heater and capable of being sealed. When stirring was carried out at a rotation speed of the stirring blade of 300 rpm, no resin precipitation was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 60 minutes, and then the heater was turned off and naturally cooled. When the internal temperature was lowered to 80 ° C., the pressure in the system was gradually reduced to remove tetrahydrofuran and water. After removing 250 g or more of tetrahydrofuran and water, when the system temperature reached 35 ° C., water was added to adjust the concentration of the acid-modified polyolefin resin in the aqueous dispersion to 20% by mass. It filtered under pressure with the filter made from the product, and obtained the milky white uniform acid-modified polyolefin resin aqueous dispersion (E-3).

(E-4 production of aqueous dispersion of polyacrylic resin)
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler was charged with 250 g of ion-exchanged water and purged with nitrogen for 1 hour while stirring. To this, 1.5 g of ammonium persulfate (polymerization initiator) was added, the temperature was adjusted to 60 ° C., and then 500 g of n-butyl acrylate, 50 g of isobutyl methacrylate, 10 g of acrylic acid, n-dodecyl mercaptan (chain transfer agent). 5 g and 20 g of sulfosuccinic acid diester ammonium salt emulsified with 120 g of water were added dropwise over 3 hours to effect emulsion polymerization. Subsequently, water is added to adjust the solid content concentration in the dispersion to 20% by mass, and pressure filtration is performed with a 180 mesh stainless steel filter to obtain an aqueous dispersion of milky white uniform polyacrylic resin ( E-4) was obtained.

Example 1
E-1 is used as an aqueous dispersion of the chlorinated polyolefin resin (A), and an aqueous dispersion of an Adekabon titer HUX350 (manufactured by Adeka Corp., polyether type polyurethane resin) is used as the aqueous dispersion of the polyurethane resin (B). Body, no non-volatile aqueous dispersion aid, polyurethane resin content 30% by mass, ionic anion (hereinafter referred to as “HUX350”). Both are mixed so that the mass ratio of the chlorinated polyolefin resin (A) contained in E-1 and the polyurethane resin (B) contained in HUX350 is (A) / (B) = 95/5, and then the non-volatile component Isopropanol was added so as to have a concentration of 15% by mass to obtain a primer for footwear constituent members comprising an aqueous dispersion containing (A) and (B).
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Examples 2 to 5, Comparative Example 4)
The same as in Example 1 except that the mixing amount was changed so that the mass ratio of the chlorinated polyolefin resin (A) contained in E-1 and the polyurethane resin (B) contained in HUX350 was the mass ratio shown in the table. The primer for footwear constituent members was obtained by this method.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Example 6)
As an aqueous dispersion of polyurethane resin (B), Adekabon titer HUX561 (manufactured by Adeka Co., Ltd., polycarbonate type polyurethane resin aqueous dispersion, non-volatile aqueous dispersion auxiliary agent, polyurethane resin content instead of HUX350) A primer for footwear constituent members was obtained in the same manner as in Example 3 except that 40% by mass, an ionic anion (hereinafter, referred to as “HUX561”) was used.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Example 7)
As an aqueous dispersion of the polyurethane resin (B), an Adekabon titer HUX380 (manufactured by Adeka Co., Ltd., an aqueous dispersion of a polyester type polyurethane resin without a non-volatile aqueous dispersion auxiliary agent, polyurethane resin content instead of HUX350) A primer for footwear constituent members was obtained in the same manner as in Example 3 except that 38% by mass, an ionic anion (hereinafter, referred to as “HUX380”) was used.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Example 8)
A primer for footwear constituent members was obtained in the same manner as in Example 3 except that E-2 was used as the aqueous dispersion of the chlorinated polyolefin resin (A).
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

Example 9
An aqueous dispersion containing (A) and (B) was prepared in the same manner as in Example 3, and then a formic acid aqueous solution having a formic acid concentration of 0.01% by mass was added to 0.1 part by mass with respect to 100 parts by mass of the aqueous dispersion. 2 parts by mass was added and mixed with a homogenizer to obtain a footwear component primer.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Example 10)
An aqueous dispersion containing (A) and (B) was prepared in the same manner as in Example 3, and then a formic acid aqueous solution having a formic acid concentration of 0.01% by mass was added to 0.1 part by mass with respect to 100 parts by mass of the aqueous dispersion. 35 parts by mass was added and mixed with a homogenizer to obtain a footwear component primer.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Example 11)
In evaluating the primer performance of the primer for footwear members obtained in Example 3, the performance of the primer was evaluated using a test piece obtained by using CR as an adhesive instead of PU.

(Comparative Example 1)
Using E-1 which is an aqueous dispersion of chlorinated polyolefin resin (A), isopropanol is added so that the non-volatile component concentration of E-1 is 15% by mass, and chlorinated polyolefin resin (A) is contained. Thus, a primer for footwear constituent members comprising an aqueous dispersion containing no polyurethane resin was obtained.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Comparative Example 2)
E-1 was used as the aqueous dispersion of the chlorinated polyolefin resin (A), and “E-4” was used as the aqueous dispersion of the polyacrylic resin. Both were mixed so that the mass ratio of the chlorinated polyolefin resin (A) contained in E-1 and the polyacryl resin contained in E-4 was (A) / (polyacrylic resin) = 50/50, and then Isopropanol was added so that a non-volatile component density | concentration might be 15 mass%, and the primer for footwear constituent members which consists of an aqueous dispersion containing (A) and a polyacryl resin was obtained. That is, Comparative Example 2 is a footwear component primer that does not contain the polyurethane resin (B) but contains a polyacrylic resin.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Comparative Example 3)
Elite is used as an aqueous dispersion of a chlorinated polyolefin resin (A), and Eritel KT9204 (manufactured by Unitika Ltd., an aqueous dispersion of a polyester resin, a non-volatile aqueous dispersion aid) as an aqueous dispersion of a polyester resin. None, a polyester resin content of 30% by mass, an ionic anion (hereinafter referred to as “KT9204”) was used. Both were mixed so that the mass ratio of the chlorinated polyolefin resin (A) contained in E-1 and the polyester resin contained in KT9204 was (A) / (polyester resin) = 50/50, and then the concentration of nonvolatile components was Isopropanol was added so that it might become 15 mass%, and the primer for footwear components which consists of an aqueous dispersion containing (A) and a polyester resin was obtained. That is, Comparative Example 3 is a footwear constituent member primer that does not contain the polyurethane resin (B) but contains a polyester resin.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

(Comparative Example 5)
The same method as in Example 3 except that E-3 which is an aqueous dispersion of a chlorine-free acid-modified polyolefin resin was used instead of E-1 which is an aqueous dispersion of the chlorinated polyolefin resin (A). Thus, a primer for footwear constituent members was obtained.
Using the obtained footwear member primer, the characteristics of the aqueous dispersion and the performance of the primer were evaluated.

  The characteristics of the primers for footwear members used in Examples 1 to 11 and Comparative Examples 1 to 5 and the evaluation results of various performances are shown in the table.

  The primer for footwear members used in Examples 1 to 11 was excellent in adhesiveness and adhesion retention between various footwear constituent members (materials used for footwear constituent members). These performances such as adhesion and adhesion retention are notable because the types and ratios of the chlorinated polyolefin resin (A) and the polyurethane resin (B), the particle diameter of the dispersed particles, and the like are within the specific ranges defined in the present invention. The effect was confirmed. In the present invention, the condition of temperature 65 ° C. and humidity 85% RH is adopted as the evaluation of “adhesion retention in harsh environments”, which is assumed in practical use of footwear. It is a more severe condition than the harsh environment. Therefore, even if treated for 2000 hours under these conditions, good adhesiveness is maintained, which means that sufficient adhesiveness is maintained for a long time in the harsh environment assumed for practical use of footwear. Can be evaluated.

  On the other hand, since Comparative Examples 1-3 did not contain the polyurethane resin (B), in Comparative Example 4, the blending ratio of (A) / (B) was out of the scope of the present invention. Since an unmodified acid-modified polyolefin resin was used, the adhesiveness and adhesion retention were poor.

  Further, from the results of Example 11, it was confirmed that a polyurethane-based adhesive was more suitable than a chloroprene-based adhesive as an adhesive applied when the footwear member primer of the present invention was used.

Claims (8)

  A chlorinated polyolefin resin (A), a polyurethane resin (B), and a medium are contained, and the mass ratio (A / B) of the chlorinated polyolefin resin (A) and the polyurethane resin (B) is 95/5 to 20 /. The primer for footwear components characterized by being in the range of 80.   The footwear component according to claim 1, wherein the chlorinated polyolefin resin (A) contains an unsaturated carboxylic acid component, and the acid value of the chlorinated polyolefin resin (A) is in the range of 1 to 100 mgKOH / g. Primer.   Dispersed particles comprising an aqueous dispersion in which the medium is an aqueous medium, the chlorinated polyolefin resin (A) and the polyurethane resin (B) are dispersed in the aqueous medium, and the chlorinated polyolefin resin (A) and the polyurethane resin (B). The primer for footwear constituent members according to claim 1, wherein the number average particle diameter of the footwear component is 1 μm or less.   The primer for footwear constituent members according to claim 1, wherein the chlorinated polyolefin resin (A) contains 20% by mass or more of a propylene unit as an olefin component.   The primer for footwear constituent members according to any one of claims 1 to 4, which is applied to footwear constituent members made of polyolefin resin.   The footwear constituent member characterized by the primer layer obtained from the primer for footwear constituent members in any one of Claims 1-5 being laminated | stacked on at least one part of the surface.   A footwear comprising the footwear constituent member according to claim 6.   The footwear component of Claim 6 is adhere | attached in footwear by the polyurethane-type adhesive provided through the primer layer.