JP3444400B2 - Metal golf club head coating, metal golf club head coating method, and golf club - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated metal golf head body coated with a coating composed of a coating material for a metal golf club head, and more specifically, a coating having excellent long-term impact peeling resistance is a metal golf club. Sequence different specific paints for metal golf club heads that may be formed on the club head surface.
The present invention relates to a metal golf head (metal golf club head coated body) coated with a coating film formed by subsequent application .

The present invention also relates to a method for coating a metal golf club head which can obtain a coating film excellent in impact peeling resistance, and a golf club having a metal golf club head having such a coating film.

[0003]

TECHNICAL BACKGROUND OF THE INVENTION As a golf club, wood,
There are types of irons, putters, etc., but with wood etc. it is light and the flight distance of the hit ball is long, and the coating does not peel off even if it is used for a long period of time Is desirable.

Therefore, various improvements have hitherto been made on the material and shape of the golf club and on the surface coating thereof. 2. Description of the Related Art In recent years, metal golf clubs including a golf club head made of titanium or a titanium alloy (collectively referred to as “titanium golf club head”) have been attracting attention as a golf club that is light and has a long flight distance. ing.

The golf club (metal golf club) having this metal golf club head has a vinyl chloride-based, epoxy-based, thermoplastic polyester-based, thermosetting polyester-based resin for improving the aesthetic commercial value of the head. It is coated with various paints such as silicone, silicone-containing vinyl, and silicon-containing vinyl.

However, there is a problem that even if the above-mentioned paint is applied, it is difficult to adhere to various metals such as titanium and titanium alloys and alloys thereof, and the paint is easily peeled off. In particular, for golf clubs with various metal heads such as conventional stainless heads and titanium heads, a hard coating film is used to ensure impact resistance so that the coating film does not peel off even when the ball directly hits the head shell. Was.
However, for example, in the case of a titanium head or the like, the Vickers hardness of the head shell reaches 280 to 340, so that with a hard coating film, "chipping" may occur on the shell striking surface, especially at the corners.

For this reason, the appearance of a coating film in which the appearance and gloss of the head shell are ensured and flexibility and toughness are imparted has been desired. By the way, in recent years, VOC (Volatile organic compound, volatile organic compound) is used as an organic solvent released from paints in the United States, Europe, etc. in consideration of adverse effects on the human body and the global environment. A regulatory net is now in place,
There is a demand for coating non- (organic) solvent type paints on the object to be coated.

In view of the above points, the present inventors have proposed a non- (organic) solvent type paint, and when it is applied to a metal golf club head or the like, even if it is repeatedly hit for a long time, a coating film is formed. When we searched for a paint that does not peel off (impact peeling resistance) and retains its aesthetic appearance for a long time, we applied acrylic resin powder coating or polyester resin powder coating on the surface of the metal golf club head. For example, they have found that a coating film having excellent durability such as impact peeling resistance and having practically sufficient durability can be formed on the surface of the head, thus completing the present invention.

As described above, a utility model registration No. 3026170 (Japanese Utility Model Application No. 7-13) is used as a golf club in which at least the club face is coated with a silicon compound type hard coating agent and a silicone type hard coating agent.
No. 551), but when the club head and the club face are made of a metal or an alloy thereof, there is a problem that even if such a paint is applied, it is difficult to adhere and the paint is easily peeled off. .

[0010]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in appearance and gloss, and is capable of being hit continuously with a golf ball for a long time and rubbing against a lawn, the ground or the like. Also, the coating film does not chip, does not wear or peel off, scratch resistance,
It is an object of the present invention to provide a paint (composition) for a metal golf club head, which is excellent in impact peeling resistance, weather resistance, and can give a coating film that can be practically used.

The present invention is also excellent in appearance and gloss, and the coating film does not wear or peel off even after repeated hits for a long period of time, and therefore has excellent scratch resistance and impact peeling resistance, and weather resistance that can withstand long-term outdoor use. It is an object of the present invention to provide a metal head (metal golf club head coated body) coated with a coating film that can be used practically, and a metal golf club provided with the metal golf club head coated body.

It is another object of the present invention to provide a method for coating a metal golf club head which can obtain a coating film excellent in impact resistance and peeling resistance.

[0013]

[0014]

[0015]

SUMMARY OF THE INVENTION In the coated metal golf club head according to the present invention, the surface of the metal golf club head is coated with a polyester.
A coating film (undercoating film, undercoating layer) (a) made of tellur resin paint ( excluding powder paint) and acrylic resin powder paint for topcoat
And the coating film (top coating film, top coating layer) (b) formed in this order.

In the method for coating a metal golf club head according to the present invention, the surface of the metal golf club head is coated with an undercoat.
Was coated poly ester resin coating (excluding powder coating), it is characterized by applying a top coat for acrylic resin-based powder coating. These base coats preferably contain pearl or aluminum flake pigments.
Yes.

The golf club according to the present invention preferably comprises the above-mentioned metal golf club head coated body, particularly a titanium golf club head. According to the invention,
The coating film does not wear or peel off even after repeated hits for a long period of time, it has excellent abrasion resistance and impact peeling resistance, and the sole surface has scratch resistance even if it rubs against the lawn or the ground when swinging,
Provided is a paint (composition) for a metal golf club head, which has excellent weather resistance capable of withstanding long-term outdoor use and can provide a coating film that can be practically used.

Further, according to the present invention, it has flexibility and toughness, is excellent in appearance and gloss, and does not cause scratches, chips or peeling on the coating film even after repeated hits for a long period of time, and therefore wear resistance and impact resistance peeling. Provided are a metal head (metal golf club head coated body) coated with a coating film having excellent properties and capable of withstanding practical use, and a metal golf club provided with the metal golf club head coated body.

[0019]

DETAILED DESCRIPTION OF THE INVENTION A metal golf club head coating material according to the present invention, a metal golf club head coating body coated with a coating film of the coating material, a metal golf club head coating method, and a golf club will be described with reference to the drawings. A detailed explanation will be given while doing so.

FIG. 1 is a perspective view showing an embodiment of the golf club according to the present invention. In FIG. 1, numeral 10 indicates a golf club, numeral 20 indicates a grip, numeral 30 indicates a shaft, numeral 40 indicates a head, and numeral 50 indicates a face.

[Metal Golf Club Head Paint, Metal Go
Ruff Club Head Painted Body and Metal Golf Club] Examples of the material of the metal golf club head base material according to the present invention include titanium, various titanium alloys, aluminum alloys, stainless steel, and other metals or composites of different metals. it can.

The paint for the metal golf club head according to the present invention comprises an acrylic resin powder paint or a polyester resin powder paint. Further, in the coated metal golf club head according to the present invention, the surface of the metal golf club head is composed of one or more layers, for example, 3 to 4 layers of coating film. In the present invention, at least one of these layers, particularly preferably the surface layer, is covered with a coating film made of this acrylic resin-based powder coating material or polyester resin-based powder coating material.

Specifically, among such coated metal golf club heads, the following are: the undercoat layer and topcoat (the topcoat layer, the surface layer, and the four-layer structure) which are the first layers in contact with the surface of the base material. Then, the fourth layer) is made of an acrylic resin-based powder coating material or a polyester resin-based powder coating material (in this case, the base coating layers of the second layer and the third layer are formed, for example, by spray coating of a solvent-based coating material). , A dipping method or the like is adopted, and a precise and specific design is exhibited.): All layers (in the above-mentioned four-layer structure, all layers from the first layer to the fourth layer) are acrylic resin powders It is preferable that the coating film is composed of a paint or a polyester resin-based powder paint.

As described above, in the coated metal golf club head according to the present invention, the surface of the metal golf club head is coated with the coating film made of the acrylic resin powder coating material or the polyester resin powder coating material. The thickness of the entire coating film (dry film) is not particularly limited, but is, for example, about 25 to 100 μm.

A coating film obtained by applying such an acrylic resin-based powder coating material or a polyester resin-based powder coating material to the surface of a metal golf club head and curing it is excellent in impact resistance and excellent in aesthetics. Further, in a golf club having the coated metal golf club head (metal golf club head coated body), the coating does not peel off even if the golf ball is continuously hit with the golf club for a long period of time, and the impact peelability is excellent. A coating film that can be used practically can be provided.

In a preferred embodiment of the present invention, the surface of the metal golf club head 40 is coated with an acrylic resin powder coating for undercoating, a polyester resin powder coating for undercoating, and a polyester resin coating for undercoating (excluding powder coating). Or coating film consisting of urethane resin paint for undercoating (undercoating film, undercoat layer)
It is desirable that (a) and the coating film (top coating film, top coating layer) consisting of acrylic resin powder coating material for top coating or polyester resin powder coating material for top coating (b) are formed in this order. Furthermore, it is desirable that the undercoat paint is an acrylic resin-based powder paint or a polyester resin-based powder paint.

In the golf club 10 shown in FIG. 1 according to a preferred embodiment of the present invention, the club head 40 comprises the above-mentioned metal golf club head coated body, preferably an undercoat layer (a) and an overcoat layer (b). It is desirable to have a two-layer coated metal golf club head coating. In such a metal golf club head coated body, the thickness of the undercoat layer (a) is, for example, 15 to 35 depending on whether or not the intermediate layer is coated.
μm, and the thickness of the overcoat layer (b) is, for example, 10 to 30.
It is about μm. A coating film (layer) having a two-layer structure including such an undercoat layer (a) (more preferably, an undercoat layer made of an acrylic resin-based powder coating material or a polyester resin-based powder coating material) and an overcoat layer (b) In a golf club having at least a metal golf club head surface, the coating film is more difficult to peel off even if the golf ball is continuously hit for a long time, as compared with a golf club having no undercoat layer (a). It excels in durability and can be put to practical use, and its aesthetic appearance continues for a long time.

Next, an acrylic resin-based powder coating material, a polyester resin-based powder coating material, which is a coating material for the undercoat layer (a) used in the production of such a metal golf club head coated body,
First, polyester resin paints (excluding powder paints) and urethane resin paints will be described in detail.

[ Coating for Undercoat Layer (a)] <Acrylic Resin-Based Powder Coating for Undercoating> Examples of the acrylic resin-based powder coating for undercoating include acrylic resin powder, a curing catalyst, a pigment, and other optional materials. Contains ingredients, etc.

[Acrylic Resin (Powder)] As the acrylic resin, (meth) acrylic acid and its derivative and, if necessary, ethylenically unsaturated bond (C =
Examples thereof include those obtained by (co) polymerizing a C) -containing monomer and the like, and may be either thermosetting type or thermoplastic type.

As a derivative of (meth) acrylic acid,
Examples thereof include (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles.
Specific examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-.
Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Isodecyl (meth) acrylate, lauryl (meth) acrylate [dodecyl (meth) acrylate], glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, amyl (meth) acrylate, vinyl (meth) acrylate, β-methallyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethyl-α-hydroxymethyl (meth) acrylate, ethylene glycol diacrylate, glyceryl tri (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate etc. are mentioned.

Specific examples of the (meth) acrylamides include (meth) acrylamide and N-methylol acrylamide. Specific examples of the (meth) acrylonitriles include (meth) acrylonitrile and ethylcyano (meth) acrylate.

Of these, methyl (meth) acrylate and glycidyl (meth) acrylate are preferably used. Such an acrylic resin may be copolymerized with "other monomers" other than those mentioned above. Specific examples of such "other monomers" include, for example, styrene, vinyl acetate, vinyltoluene. , Maleic acid, itaconic acid, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate and other monomers containing ethylenically unsaturated bond (C = C) Can be mentioned.

Among the various monomers described above, a monomer having a functional group, for example, the above ethylenically unsaturated bond-containing monomer having a carboxyl group (--COOH), a hydroxyl group, a glycidyl group, etc., the above amides, and (meth) acrylonitriles. Are copolymerized with the above-mentioned (meth) acrylic acid or a derivative thereof, and the curing reaction of the obtained acrylic resin-based powder coating material, and with the overcoat layer applied on the undercoat layer coating material. It is considered to contribute to adherence and the like.

The average molecular weight of such an acrylic resin is
Usually 2000 to 15000, preferably 2500 to 80
The glass transition temperature Tg is usually 55 ° C or higher, preferably about 60 to 70 ° C.

As such an acrylic resin, for example, acrylic acid 20 to 80% by weight and acrylic acid ester 2 can be used.
0-80% by weight and other monomers (eg styrene, α
-Methylstyrene etc.) having a molecular weight of 3000-7000, a copolymer of 20-80% by weight of acrylic acid ester and 20-80% by weight of methyl methacrylate, A homopolymer of acrylic acid, acrylic acid ester or methyl methacrylate, having a molecular weight of 4000 to 9000, and having a molecular weight (20
And the like, and the above copolymers are preferably used.

As a method for producing such an acrylic resin powder, conventionally known methods such as a bulk polymerization method, a suspension polymerization method and a solution polymerization method can be adopted. In bulk polymerization, a monomer is (co) polymerized without using a solvent, and the obtained (co) polymer is pulverized to obtain an acrylic resin powder (powder).

In suspension polymerization, the above-mentioned (meth) acrylic acid and its derivative and other functional group-containing monomers are dispersed in an aqueous system in the presence of a stabilizer (eg, polyvinyl alcohol). By copolymerizing and then removing water, an acrylic resin powder having a particle size of several tens of μm to several mm can be obtained.

In the solution polymerization, for example, 60 to 60 parts of a monomer for copolymerization such as (meth) acrylic acid ester, fumaric acid ester, styrene and glycidyl (meth) acrylate is used.
Acrylic resin powder is obtained by solution polymerization at a temperature of about 150 ° C., distilling off the solvent, and pulverizing.

Acrylic resin-based powder coating materials containing such acrylic resin powder include, for example, acrylic resin powder, curing agent (eg, decandiacid (DDA)), pigment,
It can be obtained by mixing other additives, kneading under heat melting, then cooling and pulverizing.

In particular, in the case of a thermosetting acrylic resin powder coating, it is possible to cure it by a cross-linking reaction in addition to heat fusion, or to use both heat fusion and cross-linking reaction in combination.
In this way, particularly when curing the thermosetting acrylic resin-based powder coating, it is possible to carry out reaction curing using a curing agent,
For example, when a functional group such as a hydroxyl group is introduced into the acrylic resin, a combination with a polyisocyanate curing agent; when the acrylic resin contains a glycidyl (meth) acrylate-derived unit, an aliphatic dicarboxylic acid In combination with an acid (eg, dodecanedicarboxylic acid) curing agent; when a carboxylic acid-containing monomer derivative unit is contained, in combination with a triglycidyl isocyanurate curing agent; when a hydroxyl group-containing monomer derivative unit is contained Can be used in combination with a blocked isocyanate curing agent.

In the present invention, such an acrylic resin is usually 10 to 60 parts by weight, preferably 20 to 50 parts by weight, and particularly preferably 30 to 40 parts by weight in 100 parts by weight of the acrylic resin powder coating material. It is desirable to be included in the amount of.

When the acrylic resin powder coating material containing the acrylic resin in such an amount is used, thick film coating can be performed with a small number of coatings, and a coating film excellent in smoothness and impact peeling resistance can be obtained. Therefore, it is preferable. <Polyester resin paint for undercoating> Such polyester resin paint for undercoating is a paint containing a polyester resin as a film forming component, and is a saturated polyester resin (oil-free alkyd resin) paint that does not undergo oil modification, alkyd resin paint, unsaturated Examples thereof include polyester resin paints.
Among these, in the present invention, a saturated polyester resin coating material and an unsaturated polyester resin coating material which are excellent in adhesiveness to a metal base material, impact resistance and the like are preferable.

Saturated polyester resin (oil-free alkyd resin) paints are produced by reacting a polybasic acid (polycarboxylic acid) with a polyhydric alcohol to dehydrate and condense to produce a polyester, without modifying the fatty acid. Aromatic polycarboxylic acids and aliphatic dicarboxylic acids as polybasic acids
It is a coating material containing a resin in which the polyester main chain has flexibility by using together with and . Examples of the aromatic polycarboxylic acid include terephthalic acid and isophthalic acid.
Examples of the polyhydric alcohol include neopentyl glycol, trimethylolpropane, 1,6-hexanediol and the like.

A melamine resin or the like may be contained in such a saturated polyester resin coating material. Unsaturated polyester resin paints are usually obtained by reacting unsaturated dicarboxylic acids with glycols (polyhydric alcohols), and the polycondensation product having a copolymerizable double bond in the resulting polyester main chain is obtained. It can be obtained by dissolving it in a polymerizable monomer (vinyl compound) such as styrene. When the unsaturated polyester base coating composition is cured, the polymerizable monomer copolymerizes with the unsaturated polyester to form a three-dimensional structure and contributes to curing. During this curing, a polymerization initiator (catalyst) and an activator (reaction accelerator) are used.

Examples of the unsaturated dicarboxylic acid include maleic anhydride, fumaric acid and the like, and a saturated acid (eg, phthalic anhydride) may be used together with the unsaturated dicarboxylic acid.

Examples of glycols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and the like. As the vinyl compound (polymerizable monomer), similar to the above, for example, styrene, divinylbenzene, vinyltoluene,
Examples thereof include methyl (meth) acrylate and ethyl (meth) acrylate, with methyl (meth) acrylate being preferred.

Among the unsaturated polyester resins composed of such unsaturated dicarboxylic acid and glycols, those in which the unsaturated dicarboxylic acid is maleic anhydride and the glycols are ethylene glycol are preferable. Further, the viscosity of the unsaturated polyester resin is usually 200.
300 to 5000c at about 10000cp / 20 ° C
It is preferably p / 20 ° C.

When benzoyl peroxide is used as the polymerization initiator (catalyst), amines such as dimethylaniline are used as the activator (reaction accelerator), and methyl ethyl ketone peroxide is used as the polymerization initiator. When used, as the activator, cobalt naphthenate, cobalt octoate or the like is used.

Such an unsaturated polyester base paint may usually contain an antifouling agent, a polymerization inhibitor (stabilizer), a dehydrating agent, an anti-sagging / precipitation agent, a pigment, a solvent and the like. .

Such an unsaturated polyester base paint is, for example, an unsaturated polyester resin and a resin-containing unit (a-1) containing a polymerizable monomer during storage and transportation thereof.
And a curing agent-containing unit (b) containing a polymerization initiator (curing agent).
It can be used as a two-pack type coating composition with -1), and each unit can be mixed and used when the unsaturated polyester base coating composition is applied. In addition to the above-mentioned activator (reaction accelerator) that contributes to quick-drying properties, the pigment and the like are contained in the resin-containing unit (a-1)
And the curing agent-containing unit (b-1), or one or both of them. Further, the activator is separated as a separate unit (c-1) from both the resin-containing unit (a-1) and the curing agent-containing unit (b-1), and the units (a-1) and (b- 1)
Alternatively, it may be handled as a three-pack type of (c-1).

Usually, this unsaturated polyester base paint is dried by heating in the presence of a polymerization initiator (catalyst), and is dried at room temperature by using a polymerization initiator and a polymerization accelerator together. Especially when amines are used as the accelerator,
The resulting unsaturated polyester base paint is often curable at room temperature.

There are various types of undercoating polyester resin paints such as powder paints, water-based paints and solvent-based paints described above in detail, and powder paints and water-based paints are preferably used.

In these polyester resin coatings for undercoating, the case in which the resin contained is a saturated polyester resin will be described in more detail. In powder coatings, in many cases solid polyester resins are used at room temperature. As, for example, (a) a carboxyl group-containing polyester resin used in combination with any one of an epoxy resin, a glycidyl group-containing acrylic resin and triglycidyl isocyanurate, (b) a hydroxyl group containing a polyisocyanate to cure Examples include polyester resins.

In such a powder coating material, the softening point of the contained resin is usually about 80 to 110 ° C., and when the contained resin is the carboxyl group-containing polyester resin (a), the acid value thereof is 50. In the case of a hydroxyl group-containing polyester resin (b) of 150 mgKOH / g, the hydroxyl group value is about 30 to 80 mgKOH / g.

In the water-based paint, the resin acid value is 30 to 6
A water-soluble or water-dispersible resin obtained by neutralizing a 0 mgKOH / g resin with an amine and adding water thereto is used. When the resin has a hydroxyl group, it can be baked and cured in combination with a water-soluble melamine resin. The baking conditions are, for example, 150 to 160 ° C. and about 30 minutes.

In the solvent type paint , the hydroxyl value is 40 to 150 m.
A resin of gKOH / g is used, and it is used in combination with a melamine resin as a baking coating, or in combination with polyisocyanate as a room temperature to heat-curable coating. The baking conditions for solvent-based polyester / melamine resin paint are:
For example, about 30 minutes at 140 ° C..

In the present invention, among the various polyester resin coating materials for undercoat described above, a polyester resin powder coating material is preferably used. <Urethane Resin Paint for Undercoat> Next, the urethane resin paint for undercoat will be described.

This urethane resin paint is a paint using a resin having a urethane bond as a color-developing agent (bonding resin),
The urethane resin is obtained by reacting an isocyanate compound described later with a polyol compound.

Such urethane resin coating materials include, for example, oil-modified type, moisture-curable type, block-type, catalyst-curable type,
Examples include various curable types such as polyol curable type, and one-pack type and two-pack type. Of these, the room temperature-curable one-part or two-part type is preferable because it provides excellent coating workability, impact peel resistance, and an aesthetically pleasing coating film. Those are preferable.

The above oil-modified urethane resin coating material is a one-pack type coating material composed of isocyanate-modified drying oil. This drying oil (unsaturated fatty acid) reacts with oxygen in the air to form a coating film (cured coating film). It is formed.

The moisture-curable urethane resin coating composition is a one-part urethane prepolymer obtained by reacting glycols with an excess amount of diisocyanate, and the coating composition contains free isocyanate. Moisture in the air reacts with the isocyanate groups to form a cured coating film.

The block-type urethane resin coating composition is a polyester, an acrylic resin, or a blocked isocyanate protected by an active hydrogen compound (blocking agent) that is stable at room temperature by binding with an isocyanate group and dissociates when heated to a certain temperature or higher. Obtained by blending with a polyhydroxyl resin such as resin,
It is a one-part type, and when heated, the blocked isocyanate dissociates the isocyanate group and reacts with the polyhydroxyl resin coexisting in the coating material to form a cured coating film. Examples of the blocking agent include phenols, alcohols, lactams and oximes.

The catalyst-curable urethane resin coating is a two-component system of the prepolymer, which is used by adding a catalyst (eg, triethylenediamine) to cure the moisture by the action of moisture and to react the prepolymer with the functional groups of the catalyst. , A cured coating film is formed by a self-crosslinking reaction of isocyanate groups.

Polyol-curable urethane resin coatings include polyisocyanate compounds (eg polyisocyanate / polyhydric alcohol adducts, diisocyanate polymers) and polyhydroxyl group-containing polymer compounds [eg acrylic polyol,
It is a two-component type of polyether (hydroxyl group-containing polyether) and polyester (hydroxyl group-containing polyester), and both are mixed and coated at the time of use to form a cured coating film by a crosslinking reaction between an isocyanate group and a hydroxyl group.

As the polyhydroxyl group-containing polymer compound,
In general, those obtained by a polymerization reaction of a dicarboxylic acid and a polyol monomer and having a hydroxyl group at the molecular end are mentioned.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, sebacic acid, dimer acid and the like, and examples of the polyol monomer include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,3-butanediol, hexanetriol and tricarboxylic acid. Examples thereof include polyhydric alcohols such as methylolpropane, glycerin, pentaerythritol, and sorbitol.

As the above-mentioned polyether, the above-mentioned polyhydric alcohols, amines (eg ethylenediamine, ethanolamine, aromatic amine) and polyhydric phenols (eg phenol resin) are used as starting materials. Examples thereof include those obtained by ring-opening polymerization of alkylene oxide. Specific examples of the polyol compound include poly (propylene oxide) diol, poly (propylene oxide) triol, poly (tetramethylene oxide) diol, and ethoxylated bisphenol A.
And so on.

The isocyanate compound (polyisocyanate compound, curing agent) used in the production of the various urethane resin paints or in the curing of the urethane resin paint is generally an aromatic compound or an aliphatic compound. In particular, for example, tolylene diisocyanate (TDI), methylene bisphenyl isocyanate (MDI), hexamethylene diisocyanate (HD
I), xylylene diisocyanate (XDI), 2-chloro-1,4-phenylene diisocyanate, p-phenylene diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane tri Isocyanate, tolidine diisocyanate (TODI), xylene diisocyanate, hexamethylene diisocyanate, tetramethyl-xylylene diisocyanate (TM
XDI) and its modified products, dicyclohexylmethane diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), etc., alcohols added to these isocyanate bases, and dimers and trimers of these isocyanates (oligomers). ) Is mentioned.

These isocyanate compounds can be used alone or in combination of two or more. Stoichiometrically, the above isocyanate compound reacts with a polyol compound (eg, polyether, polyester, etc.) to form a urethane bond, and the amount of OH groups in this polyol compound and the polyisocyanate It may be used in such an amount that the NCO group amount becomes an equimolar amount, but it is not unconditionally determined because it differs depending on the curing type and the like.

The acrylic resin-based powder coating material for the undercoat layer, the polyester resin coating material for the undercoating including the polyester resin powder coating material for the undercoating, and the urethane resin coating material for the undercoating include
A pigment and other optional components may be blended.

[Other compounding ingredients] Examples of such "other compounding ingredients" include a leveling agent and the like in addition to the pigment. <Pigment> As the pigment, conventionally known various organic and inorganic pigments can be used.

Examples of inorganic color pigments include various scale-like pigments, carbon black, titanium dioxide, iron oxide, iron hydroxide, red iron oxide, chromium oxide, yellow lead, ultramarine blue, various alloys, white carbon, alumina, and melted. alumina,
Examples thereof include zinc oxide, magnetic iron oxide, boron nitride, silicon carbide and clays. Examples of organic color pigments include, for example, insoluble azo pigments, soluble azo pigments, condensed polycyclic pigments,
Examples thereof include quinacridone pigments, isoindolinone pigments, cyanine blue and cyanine green. In addition, various colorants such as dyes may also be included.

Examples of extender pigments (extending agents) include glass flakes, alumina white, aluminum hydroxide, kaolin, clay, white carbon, talc, calcium carbonates, magnesium carbonate, barium carbonate, barium sulfate and bentonite. To be In addition, various colorants such as dyes may also be included.

(Scaly Pigment) In the present invention, a coating film excellent in aesthetic appearance, particularly in metallic luster and high quality, is obtained by containing the following scale-like pigment particularly in the undercoating paint, and in some cases also in the overcoating paint. It is preferable because it can be obtained.

As the scale-like pigment, mica powder (mica),
Examples include scaly aluminum powder, copper powder, zinc dust, pearl pigment, and aluminum flake pigment, and pearl pigment and aluminum flake pigment are preferably used. These scale-like pigments may be used alone or in combination of two or more.

Specific examples of such a mica powder rough include other types of white gram, such as white peach, beniunmo, sawdown moth, sericite, vanadin ummo, illite, kuromomo, quinnemo, tetsuunmo, and chinwaldummo. , Gyorek stone, celadon stone, etc. are generally used, but ground crushed products are generally used.

Examples of the pearl pigment include pigments (including color mica) obtained by coating scaly mica with titanium oxide, iron oxide and the like. The average particle size, aspect ratio, etc. of the scale-like pigment are not particularly limited, but the average particle size is preferably 0.1 to 200.
It is desirable that the thickness is μm and the aspect ratio (ratio of long side / short side of particle) is 10 or more.

Such a pigment is usually contained in an acrylic resin powder coating for undercoating in an amount of 2 to 20% by weight, preferably 5 to 1% by weight.
It may be contained in an amount of about 0% by weight. In addition to the above-mentioned pigments, the urethane resin paint for undercoating contains various components such as the above-mentioned pigments, plasticizers (eg paraffins), polymerization inhibitors [stabilizers]. , Eg: hydroquinone, benzoquinone], anti-sagging
An anti-settling agent, a solvent, a defoaming agent, a film-forming aid, a thickener, a dispersant, a bactericide and the like may be contained. [Acrylic resin powder coating for top coating and polyester for top coating
Resin resin powder coating] As the acrylic resin powder coating for top coating and the polyester resin powder coating for top coating, the above-mentioned acrylic resin powder coating for base coating and polyester resin powder coating for base coating are usually used. Excluding the pigment, anti-settling agent and dispersant, it is used.

The above acrylic resin-based powder coating material and polyester resin-based powder coating material for topcoating are an acrylic resin-based powder coating material for undercoating, a polyester resin-based powder coating material containing a similar resin content, respectively. It is preferable because a coating film having excellent adhesion to a coating film consisting of, and having excellent gloss, designability, leveling property, and sharpness can be obtained.

Basically, except for the above points, the composition, preparation method and the like of such an acrylic resin-based powder coating material for top coating and a polyester resin-based powder coating material for top coating are basically the same. , The same as the polyester resin powder coating material.

[ Method of Coating Metallic Golf Club Head] In the method of coating a metallic golf club head according to the present invention, one layer or two or more layers are formed on the surface of the metallic golf club head.
For example, about 3 to 4 layers of coating are applied, but the acrylic resin powder coating for undercoat and the polyester resin for undercoat described above for the undercoat layer (first layer) applied on the surface of the metal golf club head base material. Polyester resin paint for undercoat or urethane resin paint for undercoat typified by powder powder paint, and then spray coating and dipping with various solvent-based paints for intermediate layers (for example, second layer, third layer) if necessary. Etc., or after applying the powder coating for the intermediate layer, the above-mentioned acrylic resin-based powder coating and polyester resin-based powder coating for the outermost layer (surface layer, top coating layer) are applied. Applying. In this case, the powder coating material is applied by a method such as a corona discharge method, a triboelectric charging method, or a flow electrolysis method.

These undercoat paints preferably contain a brightening agent such as a pearl pigment or an aluminum flake pigment. <Undercoat of acrylic resin-based powder coating> To apply (undercoat) the above-mentioned "acrylic resin-based powder coating for undercoating" to the metal golf club head that is the object to be coated, general coating of powder coating is used. A method can be adopted, and examples thereof include electrostatic adhesion (electrostatic coating) and melt adhesion (fluid immersion coating), and electrostatic coating (electrostatic powder coating) is preferable.

In the present invention, the surface of the golf club head is roughened by sandblasting, a power brush, sandpaper, etc. prior to applying the undercoat paint to the surface of the metal golf club head (base material). After carrying out, the surface of the metal golf club head base material may be cleaned by air blowing or wiping off the dirt with a cloth soaked with an organic solvent.

The undercoating of at least the surface of the metal golf club head substrate among the metal parts of such a golf club is carried out by applying an undercoating paint in an amount of 50 to 100 g / m ² and after performing the following heat fusion and the like. Dry film thickness is 20-40 μm thickness /
It is performed by applying so that the thickness is about the same.

The acrylic resin powder coating material thus adhered to the surface of the golf club head is usually 100 to 18
It is fusion-cured by heating at a temperature of about 0 ° C. for 10 to 30 minutes. In particular, in the case of a thermosetting acrylic resin-based powder coating material, it is possible to cure by a crosslinking reaction in the presence of a curing agent or the like, or to use both in combination, in addition to heat fusion. <Undercoating of Polyester Resin Paint> Next, a case will be described in which the surface of a metal golf club head is undercoated with a polyester resin paint, particularly an unsaturated polyester resin paint, in place of the above-mentioned acrylic resin powder paint for undercoating.

In the unsaturated polyester resin coating material, for example, a polymerization catalyst is added together with a pigment and the like to a resin solution comprising an unsaturated polyester resin and a reactive monomer (eg, styrene monomer), followed by heating and drying, or a polymerization accelerator. Can be used together to dry and cure at room temperature.

In this unsaturated polyester resin coating material, the copolymerization monomer functions as a solvent, so that it does not contain a solvent in particular, and a thick film can be formed without thinning.

The film thickness and the like are the same as in the case of the acrylic resin powder coating material. When the polyester resin coating material for undercoating is a powder coating material, a mixture of polyester resin, a coloring pigment, a plasticizer and the like is powdered without using a volatile dispersion medium (organic solvent or water). In this state, the surface of the metal golf club head to be coated is coated and heated at a temperature of 150 to 170 ° C. for about 30 minutes to form a uniform and flat coating film. In addition,
The coating method of the powder, (a) a method of coating the surface of the article to be heated and melted, (b) a method of coating a cold resin powder on the surface of the article to be heated, (c) by electrostatic coating There are various methods such as a method of attaching a powder and heating to form a coating film, and (d) a combination thereof. <Undercoating of Urethane Resin Paint> Next, a case will be described in which the surface of the metal golf club head is undercoated with a urethane resin paint in place of the acrylic resin powder paint for undercoating.

The urethane resin coating can be dried and cured at room temperature or forced drying. For example, the oil-modified type is normally dried, the humidity-cured type is normally dried under a condition of about 30% humidity, and the block type is normally dried. For the heating and isocyanate curing type, a dry curing method such as normal drying or heating is adopted.

Of these, it is desirable to crosslink the acrylic-polyester resin type polyol with isocyanate. The film thickness and the like are the same as in the case of the acrylic resin-based powder coating material. <Acrylic resin-based powder coating, polyester resin-based powder coating topcoat> Next, in the present invention, an undercoat consisting of an acrylic resin-based powder coating, a polyester resin coating represented by a polyester resin-based powder coating, or a urethane resin coating. Coating, preferably an acrylic resin-based powder coating or a polyester resin-based powder coating, on the surface of a base coating film, the acrylic resin-based powder coating for top coating or the polyester resin-based powder coating for top coating is applied. To do.

This acrylic resin-based powder coating for top coating or polyester resin-based powder coating for top coating is applied on the surface of a metal golf club head (subject) on which an undercoat coating is formed by coating and curing the undercoat. For example, 20 to 100 g / m
The amount of ² is applied (painted) so that the dry film thickness is about 20 to 40 μm / time.

The coating method of the acrylic resin-based powder coating material for the top coating and the polyester resin-based powder coating material is the same as that for the above-mentioned acrylic resin-based powder coating material for the base coating and polyester resin-based powder coating material for the base coating. You can do this.

Thus, when both the undercoat layer and the overcoat layer are coated with the same type of coating material, that is, acrylic resin powder coating material and polyester resin powder coating material, no solvent is contained in the coating material. There is no fear of adversely affecting the surface of the base metal, and the interlayer adhesion strength between the metal golf club head surface of the base material and the undercoat layer, and between the undercoat layer and the overcoat layer is excellent, and it has excellent impact peeling resistance and aesthetics. It is preferable because a coated film, a golf club head, or a golf club can be obtained.

In the metal golf club head with a coating film (metal golf club head coating body) thus formed, the undercoat paint is a polyester resin paint represented by acrylic resin powder paint, polyester resin powder paint, urethane. In any case of the resin coating material, for example, the total film thickness of the undercoat layer (undercoat coating film) formed by coating on the surface of the base material is 20 to 40.
Top coat film (top coat layer) having a thickness of about μm and made of an acrylic resin-based powder coating or the like formed by coating on the surface of the base coat film
Has a total film thickness of about 20 to 40 μm.

According to the present invention, the coating composition (composition for metal golf club heads) is such that the coating film is not peeled off even after repeated hits for a long period of time and is excellent in impact peeling resistance and can be practically used. Object) is provided.

Further, according to the present invention, the coating film is not peeled off even after repeated hits for a long period of time, and therefore, the metal head is coated with the coating film which is excellent in impact peeling resistance and can withstand practical use (metal golf club head coated body). , And a metal golf club, particularly a titanium golf club, provided with the metal golf club head coating body.

[0097]

In the present invention, an acrylic resin-based powder coating material or a polyester resin-based powder coating material is used as the coating material for the metal golf club head. The acrylic resin-based powder coating material or the polyester resin-based powder coating material is used. A metal golf club head coated with a paint has excellent wear resistance, impact peeling resistance, weather resistance, and scratch resistance of the coating film. The coating does not wear or peel off even if it is continuously struck for a long time, and the sole surface does not easily get scratched when it rubs against the lawn or the ground when swinging. Is retained and can be put to practical use.

Further, according to the present invention, the coating film is not peeled off even after repeated hits for a long period of time, and therefore, the metal head is coated with the coating film which is excellent in impact peeling resistance and can withstand practical use (metal golf club head coated body). , And a metal golf club provided with the metal golf club head coating body.

In particular, a urethane paint, a polyester resin paint typified by a polyester resin powder paint, or an acrylic resin powder paint is applied as the undercoat paint on the surface of the metal golf club head, and then an acrylic resin paint is used as the overcoat paint. It is preferable to apply the powder coating material or the polyester resin-based powder coating material because a coating film having particularly excellent impact peeling resistance can be formed on the surface of the metal golf club head. In addition, if a pearl pigment or an aluminum flake pigment is added to these undercoat paints and, if necessary, also to the topcoat paints, the metallic luster of the head surface is increased and the aesthetic value is further improved. You get a club.

[0100]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The test methods used in the following Examples and Comparative Examples are as follows. <Test method> [Adhesiveness] JIS specified in Japanese Industrial Standards (JIS)
K5400 "JIS general test method" standard "JIS
According to "K5400 8.5.2", the "state of scratches" generated on the test piece was observed and the adhesiveness was evaluated.

<Evaluation Criteria> 10 points: Each cut is thin and smooth on both sides, and there is no peeling at each intersection of cuts and each square .

8 points: There was slight peeling at the intersection of the cuts, there was no peeling at every square, and the area of the defective portion was within 5% of the total square area. 6 points: There was peeling on both sides of the cut and the intersection, and the area of the defective portion was more than 5% to 15% of the total square area.

4 points: The width of peeling due to cuts is wide, and the area of the defective portion exceeds 15 to 35% or less of the total square area. 2 points: The area of peeling due to cuts is wider than 4 points, and the area of the defective portion is more than 35% to less than 65% of the total square area.

0 point: The area of peeling is 6 of the total square area.
5% or more. [Impact resistance] The impact resistance was evaluated according to "JIS K5400 8.3.2". [Accelerated weather resistance] Accelerated weather resistance was evaluated according to "JIS K5400 9.8.1". [Salt Water Spray Resistance] The salt water spray resistance was evaluated according to “JIS K5400 9.1”. [Abrasion resistance] For the abrasion resistance, refer to the golf club 10 described above.
Also, golf clubs each having a shaft and a grip assembled to the head of Comparative Example 1 were mounted on actual hitting robots and hit at a center speed of 10,000 times at a head speed of 45 m / s. The amount of wear of the coating film applied on the surface was visually observed.

[0106]

Embodiment 1 FIG. 1 shows a golf club 10 according to the present invention, and a head 40 is mounted on the golf club 10.

The head 40 has a two-layer undercoat layer (a) made of a polyester resin paint for undercoating having the following composition on the surface of a head base material made of titanium alloy. / Curing: 150 ℃ x 20 minutes)
Formed on the surface of the undercoat layer (a) by a coating and curing method (coating: spraying) Coating / curing: 170 ° C x 30 minutes)
(1) a first undercoat layer / a second undercoat layer / a top coat layer), which comprises a metal golf club head coated body, wherein the undercoat layer (a)
Has a total thickness of 15 μm, and the thickness of the overcoat layer (b) is 1
It is 5 μm, and the total thickness of the undercoat layer (a) and the overcoat layer (b) is 30 μm. The polyester resin paint for undercoat contains 5% by weight of a pearl pigment.

[0108] attached to the said head 40, which is attached to the golf club 10, was painted evaluation test by the above evaluation methods. <Compound composition of the first polyester resin coating for undercoat> Oil-free polyester resin varnish 48.2% by weight Melamine resin varnish 11.6% by weight Epoxy resin varnish 5.7% by weight Solvent 23.7% by weight Glittering agent 8.3% by weight % Pigment 0.3% by weight Additive 2.2% by weight (total 100% by weight) <Composition composition of second polyester resin coating for undercoat> The same composition as the first polyester resin coating for undercoat. <Compound composition of acrylic resin powder coating for top coating> Acrylic resin powder "Findick A-207S" (manufactured by Dainippon Ink and Chemicals, Inc.) 85% by weight Curing agent "DDA" (Ube Industries ( 14.5 wt% leveling agent "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 wt% The results are shown in Table 1.

[0109]

Comparative Example 1 A golf club was prepared in the same manner as in Example 1 except that a solvent-type polyester resin-based coating material for top coating was used in place of the acrylic resin-based powder coating material for top coating. The same test as 1 was performed. The composition of the solvent-type top- coating polyester resin coating used in Comparative Example 1 was the same as that of the first undercoating polyester-resin composition without adding a glittering agent to 100% by weight. . The polyester resin paint for undercoat contains 5% by weight of a pearl pigment.

The results are shown in Table 1.

[0111]

[Table 1]

According to Table 1, the head 40 of Example 1 showing a preferred embodiment of the present invention is superior in adhesion of coating film and impact resistance as compared with the conventional head (Comparative Example 1). , The coating does not wear or peel off even after repeated hits for a long time. Also,
Even if used outdoors for a long time, color fading, deterioration, rust, etc. do not occur, so it can be seen that it is possible to provide a golf club that the user can use with peace of mind.

[Brief description of drawings]

FIG. 1 is a perspective view of a golf club according to an embodiment of the present invention.

[Explanation of symbols]

10 ... Golf club, 20 ... Grip, 30 ... ・ Shaft, 40 ... Head, 50 ... Face.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoo Yoshida, Yasu Town, Yasu-gun, Shiga 7 2306 Mikami, China Paint Co., Ltd. (72) Inventor Tadashi Kurata, Yasu-cho, Yasu-gun, Shiga Prefecture 7th, China Paint Co., Ltd., 2306, Mikami (72) Inventor, Koji Morimoto, 7th, China Paint Co., Ltd., 2306, Misu, Yasu-cho, Yasu-gun, Shiga (56) Reference JP-A-8-257177 ( JP, A) Senichi Masuda, Powder Coating Technology, Stock Coating Technology Center, Co., Ltd., June 20, 1977, pp. 227-234 (58) Fields investigated (Int.Cl. ⁷ , DB name) A63B 53/04 C09D 5 / 03,133 / 04,167 / 00

Claims (5)

(57) [Claims] 1. A coating film (a) made of a polyester resin paint (excluding powder paint) for undercoating and a coating film (b) made of an acrylic resin powder paint for topcoating on the surface of a metal golf club head. ) And are formed in this order, a metal golf club head coated body. The method according to claim 2, wherein the undercoat paint, claims, characterized in that it contains the pearl pigment or an aluminum flake pigment
Item 1. A coated body according to item 1 . 3. A metal golf club characterized in that a surface of a metal golf club head is coated with a polyester resin coating material (excluding powder coating material) for undercoating, and then an acrylic resin powder coating material for topcoating is applied thereto. How to paint the club head. The method according to claim 4, wherein the undercoat paint, claims, characterized in that it contains the pearl pigment or an aluminum flake pigment
Item 3. The method according to Item 3 . 5. A golf club comprising the metal golf club head coated body according to any one of claims 1 and 2 .