JPH08309948A - Pattern paper sheet - Google Patents

Abstract

PURPOSE: To obtain a pattern paper sheet for holding stable sticking strength for a long time without impairing heat sealability and water solubility by using water soluble polyurethane resin having specified content of oxyethylene unit as a water soluble resin film layer provided on one surface of paper. CONSTITUTION: A water soluble resin film is formed of water soluble polyurethane resin derived of water soluble polyoxyalkylenepolyol and organic polyisocyanate and having at least 60wt.% of the content of oxyethylene unit. The polyoxyalkylenepolyol includes, for example, ethylene oxide homopolymer, and EO/propylene oxide copolymer. The polyisocyanate preferably includes diisocyanate and the like and crude diphenylmethane diisocyanate, or particularly preferably MDI, IDI, IPDI and HDI. The the water soluble polyurethane resin film is obtained by coating the non-drafting surface of a pattern paper sheet with water solution of urethane resin or solvent solution of methanol by an air knife coater or a bar coater.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern paper used for tailoring clothes and the like. More specifically, the present invention relates to a paper pattern paper which can be easily removed from the cloth.

[0002]

2. Description of the Related Art Heretofore, there has been known a method in which a pattern is placed on the back surface of the cloth and stapled around the cloth in order to fix the cloth on the pattern in the tailoring process of clothes and the like. However, after cutting, from the viewpoint of safety, the complicated work of completely removing the stapler needle is required, and the problem that the fabric value is reduced by damaging the fabric at the tip of the staple during removal, or the stapler However, since the fixing is not perfect, there are many problems such as a dimensional error due to the deviation of the pattern paper when cutting. For the purpose of improving this drawback, a method of temporarily fixing by heat sealing using a paper pattern coated with a water-soluble polyester resin obtained by reacting polyoxyalkylene glycol and divalent carboxylic acid on the paper surface is proposed. (For example, Japanese Patent Laid-Open No. 7-97703).

[0003]

However, the one coated with the above water-soluble polyester resin is easy to bond by heat sealing, and the resin partially attached to the cloth is completely removed in the washing step after sewing. However, it has the advantage that it can be released from the troublesome removal work such as in the case of stapling, but if the pattern paper is left for a long time, especially in high humidity, it will adhere to the fabric. Since the fixing property is deteriorated and the fixing is incomplete, there is a problem that a dimensional error due to the displacement of the pattern paper during cutting becomes large. An object of the present invention is to provide a pattern paper that solves the above-mentioned drawbacks found in conventional pattern paper, that is, a pattern paper that maintains stable adhesive strength for a long time without impairing heat sealability and water solubility. It is in.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have solved the drawbacks of the conventional pattern paper by arranging a specific water-soluble polyurethane resin film layer on the paper. The present invention has been accomplished by finding that a pattern paper that can be obtained is obtained. That is, the present invention relates to a pattern paper having a water-soluble resin film layer provided on one surface of the paper, wherein the water-soluble resin film is derived from a water-soluble polyoxyalkylene polyol (A) and an organic polyisocyanate (B). A pattern paper comprising a water-soluble polyurethane resin (C) having an oxyethylene unit content of at least 60% by weight.

In the present invention, examples of the water-soluble polyoxyalkylene polyol (A) include ethylene oxide (hereinafter abbreviated as EO) homopolymer; EO / propylene oxide (hereinafter abbreviated as PO) copolymer; hydroxyl group Compound (a) having EO alone or EO and other alkylene oxide [PO, 1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, alkylene oxide substitution product (epichlorohydrin, styrene oxide, etc.)] And a compound obtained by co-adding; and a mixture of two or more thereof.

Examples of the above (a) include polyhydric alcohols (ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polypropylene glycol, polytetramethylene ether glycol, polybutadiene glycol, polycaprolactone polyol, dimethylolpropionic acid ( Salt), glycerin, trimethylolpropane, trimethylolethane,
Pentaerythritol, sorbitol, sucrose, etc.);
Polyhydric phenols (hydroquinone, catechol, etc.);
Bisphenols (bisphenol A, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol S, etc.); water; and a mixture of two or more thereof. Of these, preferred are ethylene glycol, propylene glycol and water.

The addition mode when other alkylene oxide is used together with EO is preferably block addition,
The terminal portion of the polyoxyalkylene chain constituting (A) is particularly preferably a hydroxyethyl group from the viewpoint of reactivity with polyisocyanate. EO and EO
The average oxyethylene unit content in (A) when using an alkylene oxide other than the above is usually 65% by weight or more, and preferably 70% by weight or more.

Particularly preferable ones exemplified above as (A) are polyethylene glycol and EO /
It is a PO copolymer.

The number average molecular weight of (A) is usually 1,000 to
It is 30,000, preferably 2,000 to 25,000. When the number average molecular weight of (A) is less than 1,000, the polyurethane resin is poorly soluble in water, and when it exceeds 30,000, the reactivity with the polyisocyanate (C) becomes poor and a polyurethane resin having the desired performance is obtained. Becomes difficult.

In addition to the above (A) as a polyol component constituting the water-soluble polyurethane resin (C), if necessary, a compound having another hydroxyl group within a range not impairing the water solubility of (C) (however, (Excluding water) can be used together. Examples of the other compound having a hydroxyl group include the compound having a hydroxyl group (excluding water) exemplified as the above (a). The amount of the compound used is usually 10% by weight based on (A)
It is the following.

As the organic polyisocyanate (B),
For example, 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6
-Tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), ethylene diisocyanate,
Diisocyanates such as 1,5-naphthylene diisocyanate, 4,4′-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and xylylene diisocyanate; reaction products of tolylene diisocyanate and trimethylol propane A polyphenylmethane polyisocyanate obtained by phosgenating a polyamine obtained by reacting aniline with formaldehyde in the presence of hydrochloric acid; a crude polyisocyanate obtained by these production steps; and a mixture of two or more thereof. You can Among these, preferred are diisocyanates and crude diphenylmethane diisocyanate, and particularly preferred are MDI, TDI, IPDI and HDI.

In the present invention, the hydroxyl group of (A) and (B)
The equivalent ratio of the isocyanate group (hereinafter referred to as NCO group) is usually 1: (0.8 to 1.0), preferably 1:
(0.9 to 0.98). If the NCO group is less than 0.8 equivalent, the molecular weight of (C) will be low, and sufficient adhesive strength cannot be obtained between the paper and the tailoring fabric, causing slippage and peeling. The residual NCO group reacts with water in an aqueous solution to crosslink and reduce the water solubility of the urethane resin, which is not preferable from the viewpoint of detergency.

The weight average molecular weight of the water-soluble polyurethane resin (C) in the present invention is usually 20,000 to 50.
30,000, preferably 30,000 to 400,000
Is. When the weight average molecular weight is less than 20,000, the adhesive strength is reduced, and when it exceeds 500,000, the adhesive strength is increased, and it becomes difficult to remove the cloth from the paper.

The content of oxyethylene units in (C) is usually at least 60% by weight, preferably at least 80%.
% By weight. If the content of oxyethylene units in (C) is less than 60% by weight, the water solubility will be insufficient.

The method for producing (C) is not particularly limited,
It can be obtained by reacting (A) and (B) by an ordinary method for producing a polyurethane resin (one-shot method or multi-step method). The reaction temperature for urethanization is usually 30 to
The temperature is 200 ° C, preferably 50 to 180 ° C. The reaction time is usually 0.1 to 30 hours, preferably 0.1 to 8 hours. The urethanization reaction is usually performed in a solventless system,
If necessary, it may be carried out in an organic solvent inert to isocyanate. Examples of the organic solvent include acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, toluene, dioxane and the like. When a solvent is used, the solvent is usually distilled off after the reaction to obtain the desired (C)
Get.

The water-soluble polyurethane resin (C) can be used in combination with various water-soluble resins or water-dispersible resins, if necessary. Examples of the other water-soluble resin or water-dispersible resin include polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid salt, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, vinyl acetate polymer. , Ethylene-vinyl acetate copolymers and mixtures of two or more thereof. The ratio of the water-soluble resin or the water-dispersible resin when used in combination is not particularly limited, but is usually 50% or less, preferably 20% or less with respect to the weight of (C).

The paper used for the pattern paper of the present invention is not particularly limited as long as it is used for the conventional pattern paper, and various types such as high quality paper, foam paper, and glossy paper can be used. . In the case of fine paper or foam paper, a resin film layer is formed on the back surface of the paper, and in the case of single-glossy paper, it is formed on a non-smooth surface.

In the paper pattern paper of the present invention, the water-soluble polyurethane resin film is formed from an aqueous solution of the above urethane resin or a solvent solution such as methanol on the non-drawing drawing of the paper pattern paper such as an air coater, a bar coater, a roll coater and a blade coater. After being coated by the above method, it is formed by being dried and solidified by a heating roll, blowing drying, or the like. In addition to coating method, T
It is also possible to obtain the pattern paper of the present invention by preparing it by a die method, an inflation method, a solution casting method, a calender method, etc., and heat-bonding the film and the paper to melt-bond them. Further, the film and the paper may be simply superposed without adhering. The thickness of the water-soluble polyurethane resin film is not particularly limited, but is usually 5 to 100 μm, preferably 10 to 50.
μm.

The following is an example of how to use the pattern paper of the present invention. That is, in the polyurethane resin film layer of the paper pattern paper of the present invention, a tailoring cloth with a heat sealer,
After hot-melt adhesion using a heating device such as an iron, cutting and removal are performed. Heat seal temperature is usually 80 ℃
-180 degreeC, Preferably it is 100-160 degreeC. Within this temperature range, the fabric can be easily removed without damaging it. Since the polyurethane resin partially attached to the tailored product that has been removed and sewn is water-soluble, it can be completely removed in the final water washing step, and a sewn product with a very good finished appearance can be obtained.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, "part" means part by weight and "%" means% by weight.

Synthesis Example 1 Polyethylene glycol (number average molecular weight 8,000) 1
A water-soluble polyurethane resin [1] was obtained by reacting 00 parts and 2.05 parts of HDI at 170 ° C. for 5 hours. The [1]
The weight average molecular weight by gel permeation chromatography (the same applies hereinafter) was 85,000.

Synthesis Example 2 Polyethylene glycol (number average molecular weight 20,000)
100 parts, polyethylene glycol (number average molecular weight 8,
000) 100 parts, propylene glycol 2 parts and M
10.6 parts of DI was reacted at 180 ° C. for 3 hours to obtain a water-soluble polyurethane resin [2]. The weight average molecular weight of the [2] was 72,000.

Synthesis Example 3 Polyethylene glycol (number average molecular weight 20,000)
90 parts, polyoxyethylene oxypropylene glycol [polypropylene glycol (number average molecular weight 3,50
0) with EO added; number average molecular weight 15,000
0] 10 parts, polytetramethylene ether glycol (number average molecular weight 1,000) 3 parts and TDI 1.4 parts were reacted at 160 ° C. for 5 hours to obtain a water-soluble polyurethane resin [3]. The weight average molecular weight of the [3] is 93,000
It was 0.

Synthesis Example 4 Polyoxyethylene oxypropylene glycol [polypropylene glycol (number average molecular weight 1,700) E
O added; 100 parts of number average molecular weight 8,500] and 2.5 parts of IPDI are reacted at 170 ° C. for 5 hours,
A water-soluble polyurethane resin [4] was obtained. The weight average molecular weight of the [4] was 69,000.

Synthesis Example 5 200 parts of polyoxyalkylene polyol [glycerin added with EO; 30,000 number average molecular weight] and 1.6 parts of MDI are reacted at 150 ° C. for 8 hours to give a water-soluble urethane resin [5]. Obtained. The weight average molecular weight of the [5] was 64,000.

Synthesis Example 6 Polyoxyalkylene polyol [Glycerin with EO added; number average molecular weight 30,000] 150 parts,
18 parts propylene glycol 1 part and HDI 3.0 parts
Water-soluble polyurethane resin [6] after reacting at 0 ° C for 8 hours
I got The weight average molecular weight of the [6] was 71,000.

Comparative Synthesis Example 1 Polyethylene glycol (molecular weight 20,000) 200
Part and 1.94 parts of dimethyl terephthalic acid were subjected to a usual condensation reaction to obtain a water-soluble polyester resin [7]. The weight average molecular weight of the [7] was 82,000.

Comparative Synthesis Example 2 Polyoxyethylene oxypropylene glycol [polypropylene glycol (number average molecular weight 2,000) E
O added; number average molecular weight 20,000] 200
And a dimethylphthalic acid (1.94 parts) were subjected to a conventional condensation reaction to obtain a water-soluble polyester resin [8].
The weight average molecular weight of the [8] was 77,000.

Examples 1 to 6 and Comparative Examples 1 and 2 Water-soluble urethane resins [1] to [6] obtained in Synthesis Examples 1 to 6
Each of these aqueous solutions (concentration: 10%) was used to coat the back surface of the high-quality paper so that the solid content would be 20 g / m ² .
After drying by blast drying, the pattern paper of the present invention was produced (Examples 1 to 6). As a comparative example, the water-soluble polyesters [7] and [8] obtained in Comparative Synthesis Examples 1 and 2, respectively, were used and treated under the same conditions as in the example to prepare a comparative paper pattern (comparative). Examples 1 and 2). Next, these pattern papers were placed in a constant temperature / humidity atmosphere of 20 ° C. and 80%, taken out after 1 day and 3 days, and a cloth (cotton jeans) was applied to the water-soluble resin coated surface of the pattern paper, Two
Adhesive strength was measured for the pieces that were heat-sealed at 150 ° C. for 10 seconds at a sealing pressure of 0 g / cm ² (the ones cut into 50 mm were used as test pieces). The results of these measurements are shown in Table 1. If the adhesive strength is 20 g / 50 mm or less, it may be easily separated during the cutting process, and it is determined that the adhesive strength is not in the actual use level.

[0030]

[Table 1]

[0031]

EFFECT OF THE INVENTION The pattern paper of the present invention has a slight decrease in adhesive strength over time as compared with the pattern paper using the conventional water-soluble polyester resin, and retains excellent quality for a long period of time. In particular, by using the pattern paper of the present invention,
Trouble such as falling off from the cloth before the cutting process is solved, and dimensional error does not occur in the tailored product, and high-quality tailoring work is possible. Further, it is extremely easy to remove after cutting, and even if it partially adheres to the tailoring fabric, it can be easily removed in the final washing step because it is water-soluble.

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Claims (3)

[Claims] 1. A pattern paper comprising a paper and a water-soluble resin film layer provided on one surface thereof, wherein the water-soluble resin film is derived from a water-soluble polyoxyalkylene polyol (A) and an organic polyisocyanate (B). A pattern paper comprising a water-soluble polyurethane resin (C) having an oxyethylene unit content of at least 60% by weight. 2. The paper pattern paper according to claim 1, wherein (A) is an ethylene oxide homopolymer and / or a block copolymer of ethylene oxide and propylene oxide. 3. The pattern paper according to claim 1, wherein (B) is at least one member selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.