JPS61228030A - Agent for primer coating - Google Patents

Abstract

PURPOSE:To provide the titled coating agent for PET film, etc., having excellent adhesivity to the adherend applied to a primer layer and giving excellent antiblocking property and durability, by adding a specific water-based polyester polyurethane resin to a high polymer. CONSTITUTION:The objective coating agent can be produced by producing (A) a high polymer from (a) a polyester polyol consisting of (i) an acid component composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic dicarboxylic acid at a weight ratio of 70/30-10/90 and (ii) a glycol component, (b) a polyisocyanate compound and if necessary (c) a chain extender, and compounding the polymer A with (B) a water-based polyester polyurethane resin containing 0.5-6(wt)% pendant carboxyl group neutralized with ammonia or organic amine.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a primer coating agent, particularly a primer coating agent for polyester. Boriester, which is characterized by containing a polyester deurethane resin, and a single layer of brimer obtained by the treatment agent of the present invention have excellent adhesion to various adherends, and have anti-blocking properties and water resistance. This article concerns nine glimer coating agents with excellent properties.

<Conventional technology> Biaxially stretched? Polyester film, especially polyethylene terephthalate film (hereinafter abbreviated as PET film), has electrical insulation properties.

Due to its excellent transparency, two-dimensional stability, and toughness,
It is used in a wide range of fields such as insulating materials, drafting, photographic films, magnetic tags, metal-deposited films, and various packaging materials.

However, in general, PET 7 (lume) has a highly planarly oriented surface and therefore has poor surface activity.
Printing ink coated onto the ET film.

It has the disadvantage of poor adhesion to magnetic paints, metal vapor deposited layers, various photosensitive materials, adhesives, and the like. Therefore, in order to improve the adhesion with other base materials, the PET film surface is usually activated by various methods, and this is one of the methods! There is a limer coating.

Conventionally, water-based polyurethane resins or water-based polyester resins have been mainly considered as water-based finishing agents for brimer coating. For example, ■ Easy-adhesive polyester film (coating of water-based polyurethane resin, Special Publication No. 57-2
6236), ■Production method of easily adhesive 4-lyester film [coating of water-based polyester resin containing intramolecular nisulfonic acid groups, JP 58-1727], ■Water-soluble polyester adhesive (coating with sulfonic acid groups), Aqueous/IJ ester resin containing phosphorus compound, Japanese Patent Publication No. 5
No. 6-5476), etc.

<Problems to be Solved by the Invention> However, although water-based polyurethane resins represented by Impranil DLR and DLN have good adhesion to various adherends, they are generally not suitable for aliphatic ester polyols or polyethers. Since the main component is polyol, it basically does not have sufficient adhesion to PET film, so it is necessary to apply it to a polyester film before crystal orientation is completed and then stretch it. At present, even with such treatment, sufficient adhesion has not yet been obtained.

Furthermore, since such polyurethane resin forms a flexible film with high elasticity, it also has the disadvantage of being susceptible to blocking. On the other hand, the water-based polyester resins of ■ and ■ above are PE.
Although the adhesion to the T film is good, both contain a large amount of sulfonic acid metal bases as hydrophilic groups in order to obtain sufficient water dispersibility, and even after drying, they remain as hydrophilic groups in the film and have sufficient Water resistance cannot be obtained and under high humidity conditions, adhesion and film physical properties that can withstand practical use cannot be maintained when immersed in water, and moisture absorption tends to cause gloss and kinging over time.1 For example, primer treatment When such a PET film is rolled up, there is a problem in that the surface of the film sticks, making it extremely difficult to handle, which not only greatly reduces workability but also reduces commercial value.

Means for Solving the Problems> From this perspective, the present inventors have developed a primer coating agent for polyester film that has excellent adhesion to VcPET film, durability such as water resistance and solvent resistance, and blocking resistance. The present invention was arrived at as a result of extensive research into a primer coating agent that also has excellent adhesion to various adherends coated on a single layer of brimer.

That is, the present invention provides (A) a polyester composed of an acid component (A-1) consisting of aromatic dicargen V aliphatic (cyclic) dicarboxylic acid = 70/30 to 10010 (weight ratio) and a glycol component (A-2). A polymer obtained from a polyol, (B) a polyisocyanate compound, and (C) a chain extender if necessary, in which the indant cardexyl groups are linked by 0.5 to 6 times. The present invention provides a primer coating agent characterized by containing an aqueous-lyester I urethane resin in which the carboxyl group is neutralized with ammonia or an organic amine.

The present invention can be applied to, for example, plastic, plastic, metal (aluminum).

iron, copper), glass, paper, wood, etc! Can be used as a limer coat, especially suitable for plastics. Examples of plastics include vinyl chloride resins, polyamide resins (nylon), polyester resins, unsaturated preester resins, polyurethane resins, acrylic resins, and polyester resins are particularly preferred. In the present invention, the ester resin refers to films, sheets, etc. made of polyalkylene terephthalate as a main component, such as polyethylene terephthalate, polybutylene terephthalate, etc.
It also includes films, sheets, molded products, etc. made by copolymerizing these with other aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalene dicarboxylic acid, etc., or mixtures thereof. .

In addition, the present invention serves as a primer coating agent that is effective even for polyester resins that do not have an untreated surface.
In order to further enhance the effect of glimer coating, the primer coating agent of the present invention may not be used on polyester resins that have been previously subjected to physical or chemical treatments such as corona treatment, f-lasma treatment, or alkali treatment. do not have.

The polyester polyol used in the production of the aqueous polyester polyurethane resin of the present invention is used in order to provide the resulting polymer with excellent adhesion to PET film, as well as excellent water resistance and blocking resistance. Component (A-1) is aromatic dicarboxylic acid/fatty (3jI) group dicargenic acid = 70/30 to 100
It is essential that the polyol is mainly an aromatic polyester polyol consisting of 10 (weight ratio), and the acid component (A-
1) When the aromatic dicarboxylic acid in the content is less than 70% by weight,
Although the flexibility of the film and the resistance to impact peeling are improved, it is unsuitable because the adhesion to PET film, the water resistance, and the anti-rolling and kinging properties of the film are significantly reduced.

Aromatic dicarboxylic acids as the acid component CA-1) used in the present invention include terephthalic acid, isophthalic acid, futa, II/acid, 1,4-natutaledicarmenic acid, 2,5-natutaledicarmenic acid, 2. Aromatic dicarboxylic acids such as 6-natutaledicarmenic acid, naphthalene, pipehenyldicarboxylic acid, 1,2-bis(phenoxy)ethyl-P,P'-dicardenoic acid, and their anhydrides or ester-forming properties Examples include aromatic hydroxycarzenic acids such as derivatives, p-hydroxybenzoic acid and p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives thereof. In addition, as the aliphatic (II) group dicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sepacic acid, maleic anhydride, and hexamaric acid, 1,3-cyclopentanedicarmenic acid, Examples include alicyclic dicargens such as 1,4-cyclohexanedicarmenic acid and anhydrides or ester-forming derivatives thereof. These acids do not supply carboxyl groups.

The glycol component (A-2) is a compound having two hydroxyl groups, such as ethylene glycol, globylene glycol, 1,3-7'/9' diol, 1,4
-butanediol, 1,5-bentanediol, 1,6
- Aliphatic diols such as hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, diethylene glycol, etc.; alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexane dimetatool, bisphenols, hydroquinone; and diols such as alkylene oxide adducts thereof. In addition, the polyester polyol of the present invention is an aromatic dicarboxylic acid. acid/aliphatic (cyclic) dicardic acid = 70/30 to 10010 (weight ratio)
The present invention is not limited only to the copolymerized polyester podiol consisting of the above, and may be a mixture of an aromatic polyester-diol and an aliphatic (cyclic) polyester polyol in the above weight ratio.

Further, it is preferable that the aromatic polyester polyol is contained in an amount of 60% by weight or more as a polyester segment based on the solid content of the finally obtained aqueous polyester polyurethane resin.

The polyester podiol (A) used in the present invention is usually preferably a linear I remer, but polyfunctional components may be used within a range that does not impair the water dispersibility and adhesion of the resulting aqueous polyester polyurethane resin. does not interfere.

Such polyfunctional components include polycargenic acids such as trimellitic acid, pyromellitic acid, cyclohexa/tricarnoic acid, and their anhydrides or ester-forming derivatives; glycerin, trimethylolethane, trimethylolethane, 4-ntaerythritol, etc. The following polyols are mentioned.

It is preferable that the average molecular weight of the polyester polyol (A) of the present invention is 800 to 4000, and the molecular weight is 80 to 4000.
When it is less than 0, the isocyanate content in the polyester preurethane obtained from the polyester polyol becomes too large, resulting in a decrease in the flexibility of the film and making it brittle, and at the same time, the adhesion to the PET film is significantly reduced.
If the molecular weight exceeds 4,000, it is unsuitable because the resulting aqueous polyester polyurethane resin will have poor solubility and stability over time. A more preferable molecular weight is 100
It is 0-3000.

Chain extender (C) used as necessary in the present invention
Examples include pendant cargexyl-based diols, glycols such as ethylene glycol, diethylene glycol, propylene glycol, 1-4-butanediol, hexamethylene glycol, neopentyl glycol, and ethylene diamine, glopylene diamine, hexyl glycol, etc. Methylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane.

Examples include diamines such as piperazine and inphorondiamine, and hydrazine.

Also used in the present invention? Diincyanate compound (B
) as 2.4-) lylene diisocyanate, 2
．． 6-) lylene diisocyanate, m-7 enylene diisocyanate, p-7 enylene diisocyanate), 4
．． 4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate), 1.4-cyclohexylene diisocyanate, 4.4'-dicyclohexylmethane diisocyanate, 3 ,3'-dimethyl-4,4'
-biphenylene diisocyanate), 3.3'-diphthocyanate-4,4'-biphenylene diisocyanate, 3. a
/-Cycloro 4,4'-biphenylene diincyanate, 1,5-naphthalene diincyanate,! , 5-tetrahydronaphthalene diisocyanate and the like.

The method of introducing calgexyl groups to obtain the aqueous preester polyurethane resin having 0.5 to 6 dantocardexyl groups of the present invention may be any conventionally known method, but preferably, for example, (1) Indan obtained by copolymerizing a compound represented by the general formula HOCH2-C-CH20H (wherein R is an alkyl group having 1 to 3 carbon atoms) (■) as a glycol component when synthesizing polyester. A method using a polyester polyol having a tocargexyl base, or a method using a chain extender containing a pendant calgyl xyl group represented by the general formula CI) as a chain extender, etc. The compound represented by formula (1) is 2,2-dimethylol! Examples include robionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like.

In addition, methods for introducing indant cargoxyl groups other than those described above are disclosed in Japanese Patent Publication No. 52-3438 (a method using an aromatic diamine containing two cargelyl groups as a chain extender), and Japanese Patent Application Laid-open No. 165420/1982. Publication (Method of using half ester of polyhydroxyl compound and dicarnic acid anhydride as chain extender), Japanese Patent Publication No. 53-7479
No. 52-40677 (method of reacting excess polyalkylene polyamine with incyanate-terminated polyamine to form polyurethane urea polyamine and then adding trimellitic anhydride) Examples include a method of synthesizing a 4-reprocessed ester intermediate with a high acid value from an acid and reacting it with a polyisocyanate having an amount equal to or less than the hydroxyl group.

The amount of the compound represented by the general formula CI) used is such that at the same time a stable aqueous polyester polyurethane resin is obtained,
This is an important factor in imparting excellent water resistance to the film after drying and excellent adhesion to various adherends coated on the single layer of brimer, and the presence of pendant carxyl groups in the obtained I-diester polyurethane is Content is 0.5 to 6 (solid content) based on polyester polyurethane resin
It is necessary to carry out the reaction in an amount that falls within the weight range.

When the content of the carxyl group is less than 0.5 weight range, the water resistance of the film is significantly improved, but the stability of the resulting water-based preester polyurethane resin and the adhesion to each type of adherend are reduced. Therefore, it is inappropriate. On the other hand, if the weight exceeds 6, the adhesion to various adherends will improve, but the water resistance of the film, especially the adhesive strength when immersed in water, will be significantly reduced. The preferred range is from 0.5 to 5 h.

The aqueous polyester polyurethane resin of the present invention can be produced by any conventionally known method. Preferably, for example, the car-xyl resin of the general formula CI) is added to an organic solvent that is inert to incyanate and hydrophilic. A pendant carxyl group-containing polyester preol (A) obtained by copolymerizing a group-containing compound is reacted with a ferridiicyanate compound CB), optionally with a chain extender (C), or a specific polyester polyol , (A), the cal-xyl group-containing compound of the general formula (1) and optionally a chain extender (C) are reacted with a 4-lisocyanate compound (B) to form a urethane, and then ammonia or an organic It is produced by neutralizing it with an amine and making it aqueous (by removing the solvent under reduced pressure if necessary).Also, during the reaction with the above preisocyanate compound CB), the equivalent of the incyanate group is converted into an active hydrogen atom. By making an excess of pendant carboxyl group-containing incyanate less than! death? It can also be obtained by forming a remer, then elongating the chain in water and simultaneously neutralizing it to make it aqueous. However, the term "aqueous" here refers to stably dissolving or dispersing the resin in water.

Furthermore, in order to prevent the urethanization reaction, reaction terminators such as alcohols such as methanol, ethanol, and isopropyl alcohol; glycols such as ethylene glycol and 1,3-butanediol can also be used. .

The molecular weight of the polyester polyurethane of the present invention thus obtained is preferably from s,ooo to Zoo,000. Particularly preferably 10,000 to 50,000.

In addition to ammonia, bases that neutralize the pendant carboxyl groups used in the present invention include organic compounds such as trimethylamine, triethylamine, triethanolamine, tributylamine, triethanolamine, methyljetanolamine, dimethylethanolamine, and diethylethanolamine. Examples include amines, but in order to improve the water resistance of the film after drying, those that are water-soluble and have high volatility that easily dissociates when heated are preferred, with ammonia, trimethylamine, and triethylamine being particularly preferred.

Examples of organic solvents that are inert and hydrophilic to the isocyanate used in the present invention include ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and dimethyl esters. Examples include amides such as formamide and N-methylpyrrolidone, but water is preferably used to speed up the drying speed even when used without removing the solvent, since it is usually removed by vacuum distillation after making the polyester polyurethane aqueous. It is desirable to use a solvent with a lower boiling point.

The particle diameter of the aqueous polyester polyurethane resin of the present invention thus obtained is usually 5 μ or less, preferably 1 μ or less, and more preferably 0.1 μ or less. If this particle size is large, the particles tend to aggregate and settle, especially when diluted, which may reduce the transparency of the film, or cause the film to become uneven, especially when coating with a brimer coating with a film thickness of 1μ or less. This causes problems such as the effect of the brimer treatment not being sufficiently expressed.The aqueous I-lyester polyurethane resin of the present invention
However, in order to further improve durability such as water resistance, solvent resistance and heat resistance, or blocking resistance, amine resins, 4-oxy compounds, aziridine compounds, and polyisocyanates are used as primer coating agents. A crosslinking agent such as a compound can be used in combination. For example, amino resins include methylolated or alkoxymethylolated urea-based, melamine-based, and benzoguanamine-based resins. Examples of epoxy compounds include diglycidyl ethers of bisphenol A or hydrogenated bisphenol A and their oligomers, digsacinolesters such as terephthalic acid and succinic acid; It may also be a lactam of ethylene glycol, an active methylene compound such as acetoacetic acid ester, a polyincyanate compound which has been converted with a blocking agent such as sodium bisulfite, or an aqueous dispersion thereof.

An appropriate amount of a curing agent or accelerator can also be used in combination with these crosslinking agents.

The primer coating agent of the present invention may further include inorganic fine particles (colloidal silica) to improve blocking or slipperiness, and anionic, nonionic hydrocarbon, or fluorine-based interface to improve wettability. It is put into practical use by adding auxiliary agents such as activators or antistatic agents.

The primer coating agent obtained by the present invention is
After adjusting the resin concentration to an arbitrary resin concentration, preferably 0.1 to 20% by weight, it is coated using a conventionally known coating method, such as gravure coating, rod coating, spray I-) method, air knife coating, or roll coating. It is applied onto a polyester film by a method or the like. In order to further enhance the effect of the primer coating agent of the present invention, it may be applied during the biaxial stretching process of the polyester film, that is, before the two-wheel stretching process is completed.

<Function> The primer coating agent of the present invention formed in this manner is PET.
When coated on a film, dried, and further heat-treated if necessary, it forms a transparent, uniform film with extremely low surface blocking properties and excellent water resistance and adhesion. This primer has the feature of excellent adhesion to various adherends coated on top of the single layer, and is used for applications such as insulating materials, drafting materials, photosensitive materials, electrophotographic materials, magnetic recording materials, and packaging materials. It has excellent performance as a primer coating agent for PET film.

, Hereinafter, the present invention will be further explained with reference to Examples.
"Parts" and "Chi" are based on weight unless otherwise specified. Moreover, the present invention is not limited to this.

The methods for evaluating each physical property of the aqueous polyester preurethane resin of the present invention are shown below.

■ Adhesion to PET film The aqueous sample dispersion was applied onto a biaxially stretched PET film with a thickness of 100 μm to a dry film thickness of about 2 μm, dried at 100°C for 1 minute, and then N Co., Ltd.
A peel test was conducted using a 24m wide adhesive tape 7"K made by
Indicated by three-level evaluation.

1...Adhesion is very weak and peels off completely.

2...Peeling over 50 widths.

3... Peel off for 10 to 50 minutes.

4... Adhesive strength is quite strong, with only 1 oes peeling off.

5...The adhesive strength is very strong and does not peel off at all.

■ Adhesion to magnetic coating film A magnetic coating composition with the following composition was applied to the PET film after primer and coating obtained in (iii) above using a percoater so that the dry film thickness was approximately 10 μm. After drying at ℃ and then heat treatment at 60℃ for 1 day, a peel test was performed using adhesive tape made by Nichiban.
It is indicated by the three-level evaluation defined in ■.

"Krysgen 4216" (polyester urethane resin manufactured by Dainippon Ink and Chemicals Co., Ltd.) 225 parts "Vinyrite VAGHJ (salt pea-vinegar vinegar copolymer manufactured by Union Carbide, USA)" 40 parts cyclohexanone/methyl ethyl keto y = 1/1 ( (weight ratio) 435 parts of mixed solvent γ-Fe203 magnetic powder 35 (1) Cargan Black 12 parts Burnock D-750J (low molecular weight polyisocyanate manufactured by Dainippon Ink & Chemicals Co., Ltd.) 15 parts Lubricant 7 parts ■ Adhesion to ink The gravure ink shown below is used in place of the magnetic paint, and the procedure is the same as in (2) above except for the holes.

“CLS-709 White” (Dainippon Ink & Chemicals Co., Ltd.)
gravure ink for printing on cellophane) 50 parts toluene/ethyl acetate/MEK=1/1/1 (weight ratio)
100 parts of a mixed solvent consisting of (2) Adhesion to gelatin film The same procedure as (2) above was carried out except that an aqueous gelatin solution was used in place of the magnetic paint.

■ Non-blocking property PE obtained in above ■ after brimer coating
T 74 lumes were pasted together, a load of 10,017 cm was applied, and the film was left in an atmosphere of 40°C and 651 R, H for 24 hours, and then the film was peeled off and the adhesion was evaluated on the following three levels. Indicated by

O: There is no stickiness at all and it can be peeled off without any problems.

Δ: There is some tackiness, but there is no change in the coated surface.

×...Surface defects due to adhesion have occurred on one of the coated surfaces.

■Water resistance PE obtained in above ■ after brimer coating
After the T film was immersed in warm water at 40°C for 24 hours, a peel test was conducted using an adhesive tape manufactured by Nichiban Co., Ltd., and the results were evaluated according to the three-level evaluation defined in (2).

Preparation of polyester polyol> While introducing nitrogen gas into a reactor equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 664 parts of terephthal, 22,631 parts of isophthal, 2 parts of 1,4-butanediol,
447 parts of neopentyl glycol and 0.5 parts of sibutyltin oxide were charged and esterified at 180 to 230°C for 5 hours, followed by polycondensation reaction at 230°C for 6 hours until the acid value became <1. Then, it was cooled to 120°C, 321 parts of adipic acid and 268 parts of zomethylolglopionic acid were added, and the temperature was raised to 170°C again and reacted at this temperature for 20 hours.
A danthocargexyl group-containing polyester polyol A having an acid value of 46.5 and a hydroxyl value of 59.8 was obtained. E,G
(See Table 1).

Example 1 1880 parts of polyester polyol A was heated at 120°C under reduced pressure.
After dehydrating at 80"ct and cooling at 80"ct, 1412 parts of methyl ethyl ketone was added and dissolved with sufficient stirring.
238 parts of 4'-diphenylmethane diisocyanate was added and reacted at 70°C for 8 hours.

After the reaction is complete, cool to 40'C and add 10 ml of ammonia water.
After neutralizing by adding 65 parts, 6090 parts of water was added to make it water-soluble.

After removing methyl ethyl ketone from the resulting transparent reaction product under reduced pressure at 65°C, water was added to adjust the concentration to obtain a stable transparent colloidal dispersion with a nonvolatile content of 25%.

The particle size of this product was 0.1 μm or less. This aqueous dispersion was placed on a 100 μm PET film with a solid content of 21/m”.
After coating, the transparent dry film obtained by drying at 100° C. for 1 minute was tested for adhesion, water resistance, and anti-polishing and kinging properties. As a result, good physical properties were obtained in all cases. Furthermore, after applying monomagnetic paint, cellophane ink, and gelatin aqueous solution to the primer-treated PIT film and drying, a peel test with Cellophane Tea 7' was conducted. As a result, both the adhesive layer and the brimer layer were PET. It was confirmed that the water-based polyester polyurethane resin of the present invention had excellent adhesive properties without being peeled off from the film.Examples 2 to 4. Comparative Examples 1 to 3 Various types of IP IJ shown in Table-IK were prepared in the same manner as in Example 1.
Examples 2-4 using ester polyols. Comparative example 1
Obtain an aqueous 4-lyester 4-urethane resin of ~3. still,
In Examples 2, 3, and 4 and Comparative Examples 1 and 3, urethanization was performed using 2,2-dimethylolgropionic acid as a chain extender. Table 2Kt shows the physical properties and adhesive properties of each dry film.

In Comparative Example 1, the content of polyester segments was low, so the adhesion to the PET film was insufficient, and therefore, even when magnetic paint, cellophane, ink, and gelatin were applied, there was no peeling between the Bligh 4 layer and the PET film. This occurs and sufficient adhesion cannot be obtained.

In Comparative Example 2, since the content of aromatic dicardic acid was low, water resistance and blocking resistance were insufficient, and adhesiveness was also low.

Furthermore, in Comparative Example 6, since the molecular weight of the 4-lyester polyol is low, the resistance to impact peeling is weak and the adhesive strength is also weak. In comparison, all the aqueous dispersions of the present invention exhibit excellent physical properties and adhesive properties, and are found to be excellent as primer coating agents.

Procedural amendment (spontaneous) December 2q, 1985 Michibe Uga, Commissioner of the Patent Office 1, Indication of the case 1985 Patent Application No. 66699 Z Name of the invention Primer coating agent 5 Person making the amendment Relationship to the case Patent applicant address: 35-58 Sakashita, Itabashi-ku, Tokyo 174 (288
) Dainippon Ink & Chemicals Co., Ltd. Representative Shigeru Kuni Kawamura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Phone: Tokyo (03) 272-4511 (Main representative) )(8
876) Patent attorney Katsutoshi Takahashi 5 changed "polyester segment" to "aromatic polyester segment" in line 4 of "Detailed explanation of the invention in the specification to be amended & content of amendment (1) on page 27 of the specification tube." correct.

(2) r3 in the molecular weight column of Example 30 in Table-2 on page 29
Correct 500J to r35,0OOJ.

(3) "5" in the column of adhesiveness to PET film of Comparative Example 2 in Table 2 on page 29 is corrected to "2".

(Above) Procedural amendment (voluntary) February 7, 1985 Michibe Uga, Commissioner of the Patent Office 1, Indication of the case 1985 Patent Application No. 66699 2, Name of the invention Primer; Relationship with the case of the person making the amendment Patent applicant: 3-35-58 Sakashita, Higashiyuto Itabashi-ku, 174 (2
88) Dainippon Ink & Chemicals Co., Ltd. Representative Kawa
Shigeru Kuni Mura 4, Agent Address: Dainippon Ink Chemical Industry Co., Ltd., 3-7-20 Nihonbashi, Higashieto Chuo-ku, 103 Detailed description of the invention in the specification 8Att>4 6. Contents of amendment (1) Details In Table 2 on page 29 of the letter, r218J of inphorone diisocyanate in Example 2 is corrected to r435J.

(2) "O" in the column of anti-blocking property of Comparative Example 1 in Table 2 on page 29 is corrected to "Δ".

(3) Water resistance column “3” of Comparative Example 2 in Table 2 on page 29
” is corrected as rlJ.

(4) On page 29, i-2, in the column for adhesion to magnetic paint in Comparative Example 2, "3-4" in the column for adhesion to cellophane ink and for adhesion to gelatin was corrected to "2". O (and above) Procedural amendment June 19, 1985 Michibe Uga, Director General of the Patent Office1, Indication of the case, 1985 Patent No. 666992, Name of the invention Primer coating agent3, Person making the amendment Relationship to the incident Patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo' (288) Representative of Dainippon Ink and Chemicals Co., Ltd.
Shigekuni Kawamura.

4. Agent: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103, Japan 7. Contents of amendment (1) The statement in line 8 of member 6 of the description is as follows: Correct it like this.

"Rethane resins, acrylic resins, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, etc., among others,"

Claims (1)

[Claims] (A) Acid component consisting of aromatic dicarboxylic acid/aliphatic (cyclic) dicarboxylic acid = 70/30 to 100/0 (weight ratio) (
A-1) and a polyester polyol composed of a glycol component (A-2), (B) a polyisocyanate compound, and (C) optionally a chain extender, the polymer being obtained from A primer coating agent comprising an aqueous polyester polyurethane resin containing 0.5 to 6% by weight of pendant carboxyl groups in the molecular weight, and in which the carboxyl groups are neutralized with ammonia or an organic amine.