JP3241312B2 - Transfer film and golf ball using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer film used for transferring a predetermined design to an article and a golf ball marked by using the transfer film. The present invention relates to a transfer film that can be transferred by a thermal transfer method and a golf ball marked using the transfer film.

[0002]

2. Description of the Related Art Generally, a transfer film used for transferring a design such as a logo mark or a character to various articles is formed by printing a predetermined design on one surface of a band-shaped base film by, for example, gravure printing or screen printing. An ink layer is provided, and the above pattern is transferred to the article side by pressing a heated pad from the back surface of the base film in a state where the ink layer is positioned on the article surface. In the case of transferring a design to a golf ball, considering the situation in which the golf ball is used, it is strongly required that the transferred ink layer is less likely to be peeled off than in the case of transferring a design to another object to be transferred. You.

[0003] Generally, in the case of a golf ball, it is customary to apply a clear coating of urethane on the golf ball after the transfer of the design so as to polish and protect the ball or the design. If the adhesion between the ink layer and the urethane layer of the top coat is weak, the impact resistance at the design portion is reduced and the ink is easily peeled.

As a technique for addressing this problem, Japanese Patent Laid-Open No.
JP-89214 discloses the use of a urethane resin having a predetermined hydroxyl value for the ink. According to this, when the formation of the urethane coating film after the transfer of the ink is performed by a two-liquid reaction type spray coating, the isocyanate present in the coating liquid reacts with the hydroxyl group of the ink layer to form the urethane coating film. A new urethane bond is generated between the ink and the urethane top coat, and the adhesion or impact resistance of the ink is enhanced, making it difficult for the pattern to peel off.

[0005]

The above-mentioned publication discloses that the ink layer is thermally transferred to a golf ball using a silicone pad heated to, for example, about 130 ° C., and the transfer temperature is low. Is described. In general, when a thermal transfer method is employed in this type of transfer film, thermal damage to the transferred object, that is, a problem such as deformation of a dimple or the ball itself due to heat in the case of a golf ball, polypropylene or the like. Considering the problem of wrinkling of the design due to thermal shrinkage of the base film composed of laminated foil with glassine paper, or the photothermal cost at the time of transfer, the design can be transferred by softening the ink layer at the lowest possible temperature. It is desired to do so. In this sense, in the technology disclosed in the above-mentioned publication, since ink containing only a urethane resin having a relatively high softening temperature as a main material is used, it is considered that there is a limit in realizing a lower transfer temperature.

Accordingly, the present invention provides a transfer film which enhances the adhesion or impact resistance of the transferred design and is difficult to peel off, and which can lower the transfer temperature of the design, and performs marking using the transfer film. It is an object of the present invention to provide a golf ball.

[0007]

Means for Solving the Problems To solve the above problems, first, the invention described in claim 1 of the present application (hereinafter, referred to as "first invention") is a method in which a predetermined film to be transferred onto one surface of a base film is provided. A transfer film provided with an ink layer printed on the pattern of the above, wherein the ink layer is 0 or more
A urethane resin having a hydroxyl number of less than 0.2 ;
It is characterized by containing at least one of a polyester resin or an epoxy resin having a hydroxyl value of 60 or more and 250 or less .

[0008]

Furthermore, the invention described in claim 2 (hereinafter referred to as "second invention") is characterized in that Oite in the first shot bright, more polyethyleneimine resin in the ink layer are contained .

[0010] Then, by the invention (hereinafter referred to as "third invention") is set forth in claim 3, in the second invention, with respect to 100 parts by weight of a urethane resin, or both the least of polyester resin or epoxy resin It is characterized by containing 5 to 10 parts by weight and 0.5 to 2.0 parts by weight of polyethyleneimine resin.

On the other hand, the invention described in claims 4 to 6 is:
The present invention relates to a golf ball that has been marked using the transfer film according to the first to third aspects of the present invention.
Invention set forth in claim 4 (hereinafter referred to as " fourth invention")
The golf ball according to any one of the above,
Urethane resin having a hydroxyl value of less than 0.2
And a poly having a hydroxyl value of 60 or more and 250 or less
With at least one of ester resin or epoxy resin
A transfer filter in which an ink layer containing
It is characterized in that marking is performed by transferring the symbol by means of a lum .

[0012]

Further, the golf ball according to the invention described in claim 5 (hereinafter referred to as “ fifth invention”) is a golf ball according to the fourth aspect.
The invention is characterized in that the ink layer contains a polyethyleneimine resin.

The golf ball according to the invention described in claim 6 (hereinafter referred to as “ sixth invention”) is a golf ball according to the fifth aspect.
In the invention, the ink layer contains at least 5 to 10 parts by weight of a polyester resin or an epoxy resin and 0.5 to 2.0 parts by weight of a polyethyleneimine resin with respect to 100 parts by weight of the urethane resin. And

As described above, in the transfer film according to the first to third aspects of the present invention, the ink layer on the base film is formed not only of the urethane resin but also of a polyester resin having a lower softening temperature or a polyester resin having a lower melting point. Since the epoxy resin is contained, the softening temperature of the ink layer as a whole becomes lower than when only the urethane resin is used as the main material, and therefore, the transfer temperature when thermally transferring the pattern of the transfer film should be lowered. This makes it possible to reduce problems such as thermal damage to an object to be transferred, heat shrinkage of a base film, and photothermal costs.

On the other hand, since each of the urethane resin, polyester resin, and epoxy resin has a significant predetermined hydroxyl value, this transfer film is used particularly for transferring a pattern of a golf ball. When the urethane top coat is applied by a two-component reaction type spray coating or the like, a new urethane bond is generated between the transferred ink layer and the urethane layer applied from above, and the ink layer or the pattern is formed. The peel resistance will be improved.

In this case, the reason that the hydroxyl value of the urethane resin is 0 or more and less than 0.2 is that when the hydroxyl value becomes 0.2 or more, the softening temperature rise due to intermolecular hydrogen bonding becomes remarkable and ink becomes This is because the lowering of the softening temperature of the entire layer is hindered. Also, the reason that the hydroxyl value of the urethane resin may be 0 is the reason that the lowering of the softening temperature of the ink layer is prioritized, and the hydroxyl value of the other polyester resin or the epoxy resin is high, and the ink layer and the spray coating are not sprayed. This is because this can sufficiently compensate for the reactivity with the urethane layer.

The reason why the hydroxyl value of the polyester resin or the epoxy resin is 60 or more and 250 or less is as follows.
When the hydroxyl value is less than 60, the degree of bonding between the ink layer and the urethane layer is weakened. When the hydroxyl value is more than 250, the softening temperature rise due to intermolecular hydrogen bonding becomes remarkable and the entire ink layer becomes This is because the lowering of the softening temperature is hindered. Incidentally, the hydroxyl value of this polyester resin or epoxy resin is more preferably 140
~ 210.

Further, when a polyethyleneimine resin is contained in addition to the urethane resin, the polyester resin and the epoxy resin as in the second invention, the adhesiveness of the ink layer to the transfer object is improved.

The content of each of these components is as follows:
As in the third invention, at least one of a polyester resin and an epoxy resin is 5 to 10 parts by weight and a polyethyleneimine resin is 0.1 to 100 parts by weight of a urethane resin.
It is preferably from 5 to 2.0 parts by weight. If the amount of the polyester resin or epoxy resin is less than 5 parts by weight, the reactivity of the entire ink layer with the urethane layer and the lowering of the softening temperature cannot be sufficiently obtained. The strength and rigidity of the film decrease. On the other hand, if the amount of the polyethyleneimine resin is less than 0.5 part by weight, the effect of improving the adhesion between the ink layer and the material to be transferred provided by the resin cannot be sufficiently obtained. The effect is not so high.

As the base film used in the transfer films of the first to third inventions, there can be used a polypropylene film or a biaxially stretched polypropylene film which has been generally used, or a laminate foil of the above and a glassine paper. is there. Further, as a method of printing ink on the base film, a gravure printing method, a screen printing method, and the like, which are conventionally performed, can be adopted.

On the other hand, since the golf balls according to the fourth to sixth inventions of the present application have an ink layer having the above-mentioned composition, they have good adhesion to a urethane layer usually used as a top coat, and have a marked pattern. Excellent durability. In addition, since the transfer can be performed at a relatively low temperature of 90 ° C. to 120 ° C., there is almost no thermal deformation of the dimple shape on the golf ball surface.

The golf balls of the above inventions may be one-piece, two-piece, three-piece, other multi-layer solid golf balls, or thread-wound golf balls.

The material of the cover layer on the surface of the golf ball to be marked may be an ionomer resin,
Polyurethane, polyester, polyamide, a mixture thereof and the like can be used.

Further, as a base treatment before marking,
Any known plasma treatment or chemical treatment with a chlorine-based chemical can be applied.

The marking method is not particularly limited, and a method using a known up-down transfer machine or the like can be used. The transfer temperature is 90 ° C. to 150 ° C., as the surface temperature of the silicone rubber pad in contact with the transfer film.
In particular, the transfer time is preferably from 90 ° C. to 120 ° C. and the transfer time is within 2 seconds.

Then, a clear coating with a two-component reaction type urethane resin paint is applied from above. This coating is preferably spray coating, but is not particularly limited thereto. In addition, as this urethane resin paint, a known paint can be used.

[0028]

The present invention will be described below in more detail with reference to examples.

Example 1 Preparation of Transfer Film A biaxially stretched polypropylene film having a thickness of 20 μm was used as a base film.
100 parts by weight of a polyurethane resin having a hydroxyl number of 0.1 and 8 parts of a polyester resin having a hydroxyl number of 150
Parts by weight, and 1.2 parts by weight of a polyethyleneimine resin, and further, an ink having a composition containing 10 parts by weight of carbon black as a pigment was diluted with an organic solvent, and was gravure-printed by 3 mm in length and 3 mm in width. Was printed to a thickness of 1 micrometer to produce a transfer film A according to the present invention. Similarly, transfer films B, C,
D and E were prepared. Table 1 summarizes the ink composition of each transfer film.

[0030]

[Table 1] -Thermal transfer of the design Using these transfer films A, B, C, D, and E, the design was thermally transferred to a typical golf ball on the surface of a plasma-treated ionomer resin. Transfer temperature is 90
° C, and pressure-bonded with a silicon pad for 1 second. Next, a top coat of urethane is applied to the entire golf ball by spray coating of a two-liquid reaction type from above the transferred pattern,
Dried and cured.

Impact Test and Wear Resistance Test The golf ball obtained as described above was subjected to a speed of 140 kph.
The impact resistance test was conducted by colliding the steel sheet 200 times with
Further, the abrasion resistance test was carried out by stirring with sand for 2 hours, and the degree of peeling or deficiency of the design part was visually observed.
The letter "H" transferred from D and E was also displayed on the golf ball surface in a good contact state without becoming indecipherable.

Example 2 Preparation of Golf Ball A two-piece ball obtained by coating a core made of a crosslinked rubber mainly composed of polybutadiene rubber with a cover material mainly composed of an ionomer resin having a Shore D hardness of 65 to a thickness of 2 mm was used. Multiple were prepared. The surface of this ball was subjected to plasma surface treatment in the same manner as the ball used in Example 1.

For each of the above balls, the same ball as the transfer film E prepared in Example 1 was used and 3 mm in length.
× An "H" character mark having a size of 3 mm in width was transferred.

The transfer temperature is 90 ° C., 100 ° C., 120 ° C.,
Either 130 ° C. or 150 ° C., and other conditions were the same as in Example 1. In addition, the transfer temperature measured the temperature of the surface of the silicon pad which directly contacts a transfer film with the surface thermometer.

Evaluation of Transferability and Adhesion At this stage, it was visually observed and judged whether or not the marked characters were completely transferred for 20 balls. Table 2 shows the results.

Next, as an evaluation of the adhesion of the marking ink, a peeling test using a cellophane tape was performed. As the cellophane tape, a clear tape of Sumitomo 3M Limited was used. The results are also shown in Table 2.

Further, the same urethane clear paint as that used in Example 1 was spray-coated on the ball with the above-mentioned marking, and the coated state of the marking portion of the ball was observed.

Durability Test Next, the above balls were subjected to a durability test for the following marks.

(Collision test)
Using one wood, the target was made of cloth at a head speed of 45 m / s and repeatedly hit 200 times, and the degree of marking damage was visually determined. Table 3 shows the results.

(Sand Abrasion Test) Sand used for a bunker in a golf course was put into a porcelain ball mill, and the ball was put into the sand mill and rotated for 2 hours. Thereafter, the ball was taken out, and peeling and damage of the marking portion were visually evaluated according to the following criteria. Table 3 shows the results.

(Sand Water Abrasion Test) Bunker sand and water of the same weight were put in a porcelain ball mill and rotated for 3 hours, and peeling and damage of the marking portion were visually evaluated. The evaluation criteria were the same as in the above sand abrasion test. Table 3 shows the results.

In Table 3, "O" indicates that there was no change or chipping of the mark before and after the test, and "X" indicates that the mark was peeled or chipped by the test.

Comparative Example As a transfer film, a film was used in which an ink layer having a composition containing 100 parts by weight of a polyurethane resin having a hydroxyl value of 3 and 10 parts by weight of carbon black was provided on the same base film as in Example 1. Other than that, a ball prepared by the same method as in Example 2 was prepared as a comparative example, and the above various durability tests were performed. The results are shown in Tables 2 and 3 together with Example 2.

From the above results, as is apparent from Table 2, it was confirmed that the ink of Example 2 was excellent not only in transferability and adhesiveness but also capable of transferring at a low temperature.

Regarding the change in the dimple shape of the ball after the transfer, deformation was observed at a transfer temperature of 150 ° C. and slight deformation was observed at 130 ° C.
No change was observed at 00 ° C and 90 ° C. Therefore, the ink of the embodiment capable of transferring at a low temperature is advantageous in terms of the influence on the dimple.

Further, with respect to the wettability of the clear coating, neither the ball of Example 2 nor the ball of the comparative example had repelling at the marking portion, and both of them had no problem.

As is clear from Table 3, Example 2
Regarding the durability of the marking portion of the ball, good results were obtained in all the tests, and it was confirmed that the durability when transferred at a low temperature was particularly superior to the comparative example.

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

As described above, the transfer film according to the present invention contains a low-melting polyester resin, an epoxy resin or a mixture thereof having a low softening temperature in the ink layer on the base film. The softening temperature of the ink layer is lowered as a whole, and as a result, the pattern can be transferred at a low transfer temperature, resulting in thermal damage such as deformation to the transferred object, heat shrinkage of the base film, or thermal transfer. Problems such as the cost of light and heat required are reduced.

Since the polyester resin and the epoxy resin also have a large hydroxyl value, when the two-component reaction type urethane coating is formed after the transfer of the pattern, the ink layer and the urethane coating are used. Urethane bonds are also generated between them, making it difficult for the design to peel off.

Therefore, the golf ball according to the present invention, which is marked by using the above-mentioned transfer film, has no thermal deformation of the dimple shape due to the transfer, has a dimple shape very close to the design value, and has good flight characteristics. Will have.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ken Hiragawa 135 Shimo-Toba Jinokoshi-cho, Fushimi-ku, Kyoto City Inside Showa Ink Industries Co., Ltd. (72) Inventor Ryuhei Kameya 1-14-1 Harimacho, Abeno-ku, Osaka-shi No. Within Kameya Sangyo Co., Ltd. (72) Inventor Susumu Muta Inside 20, Onohara, Chichibu City, Saitama Prefecture, Japan Bridge Sports Co., Ltd. Document JP-A-7-89214 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B44C 1/165-1/17

Claims (6)

(57) [Claims] 1. A transfer film provided with an ink layer printed on a predetermined pattern to be transferred on one surface of a base film, wherein the ink layer has a hydroxyl value of 0 or more and less than 0.2. Urethane resin, 60 or more 25
A transfer film comprising a polyester resin or an epoxy resin having a hydroxyl value of 0 or less . 2. The ink layer further comprises a polyethylene imine tree.
The transfer film according to claim 1, wherein the transfer film contains a fat . (3) 100 parts by weight of a urethane resin,
At least one of an ester resin or an epoxy resin
5 to 10 parts by weight, 0.5% polyethyleneimine resin
The transfer film according to claim 2, wherein the content of the transfer film is from 2.0 to 2.0 parts by weight . 4. The method according to claim 1 , wherein one side of the base film has a thickness of 0 to 0.2.
A urethane resin having a hydroxyl number of less than
Polyester tree having a hydroxyl value of not more than 250
Contains at least one of fat and epoxy resin
A transfer film with an ink layer provided on a predetermined design
The marking is given by transferring the symbol
A golf ball. 5. The ink layer further comprises a polyethylene imine tree.
The golf ball according to claim 4, further comprising a fat . 6. An ink layer comprising 100 parts by weight of a urethane resin.
In contrast, at least polyester resin or epoxy resin
Also 5 to 10 parts by weight, polyethyleneimine
The golf ball according to claim 5, wherein the resin is contained in an amount of 0.5 to 2.0 parts by weight .