JPH0668099B2 - Adhesive paper for copy - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive paper for copying, and more particularly to an adhesive paper for copying in which a photosensitive drum is not contaminated during copying.

TECHNICAL BACKGROUND OF THE INVENTION AND PROBLEMS THEREOF Top paper and release paper are laminated so that a pressure-sensitive adhesive layer provided on the lower surface of the top paper and the release surface of the release paper are in contact with each other, The release paper is peeled off after a copy is made on the surface of the upper paper, and is stuck and used at a desired place.

By the way, in the pressure-sensitive adhesive paper for copying having the above-mentioned configuration, the pressure-sensitive adhesive layer provided on the lower surface of the upper paper is conventionally
Acrylic and rubber adhesives have been used. However, the adhesive paper for copying made by using such an adhesive, when contacting the photoconductor drum of the copying machine at the time of copying,
There is a serious problem that the adhesive sticking out from the end surface of the copying adhesive paper may come into contact with the drum, and the photosensitive drum of the copying machine may be contaminated with the adhesive. Further, the adhesive paper for copying is heated during the fixing of the toner, but if the adhesive has poor heat resistance, the adhesive may also squeeze out from the end surface of the adhesive paper for copying. There was also a problem that it was contaminated by the adhesive.

In order to solve such a problem, for example, JP-A-59-
In 159874 publication, there is proposed a pressure-sensitive adhesive paper for copying, which is characterized in that a paint layer for preventing the exposure of the pressure-sensitive adhesive is provided on the end face of the pressure-sensitive adhesive paper as described above.
Fiber-based derivative paints such as nitrocellulose and acetyl cellulose, organic solvent-based synthetic resin paints such as thermosetting acrylic resin and phenol formaldehyde resin, and aqueous synthetic resin paints such as vinyl acetate and styrene butadiene are used.

However, in the copying adhesive paper disclosed in JP-A-56-159874, the coating material applied to the end surface of the copying adhesive paper may penetrate into the top paper, the adhesive layer, and the release paper. There is a problem in that the end face of the pressure-sensitive adhesive paper is not sufficiently protected and the pressure-sensitive adhesive may stick out. Further, since the coating material applied to the end surface of the adhesive paper is cured by heating, there is a problem that the upper paper and the release paper are curled by the heat.

On the other hand, although it is not an adhesive paper for copying, in order to prevent the adhesive from squeezing out from the end face of the wrapping adhesive tape, the photocrosslinking sensitizer, the photoactive crosslinking agent and the vinyl-based adhesive are applied to the end face of the wrapping adhesive tape. Apply an organic solvent containing a polymer compound,
The wrapping tape that is irradiated with light is
It is disclosed in the publication. However, when trying to apply this technology to adhesive paper for copying, since an organic solvent is used, this organic solvent penetrates into the top paper or release paper of the adhesive paper, and the top paper and release paper curl. In addition, there is a problem that the organic solvent causes environmental pollution.

When a radiation-polymerizable compound such as an epoxy resin is irradiated with radiation to form a radiation-polymerized layer on the end face of the copier adhesive paper, when the copier adhesive paper is brought into contact with the photoconductor drum of the copying machine, the It has been found by the present inventors that the layer may be cracked and fallen off by being pressed against the photoconductor drum, and the photopolymerized drum may be contaminated by the dropped polymerized layer.

The inventors of the present invention have made extensive studies to solve the above problems all at once, and the problems can be solved all at once without using a solvent at all and using a specific radiation-polymerizable compound. Found that, on the end surface of the adhesive paper for copying, a radiation-polymerizable composition consisting of a radiation-polymerizable compound containing no solvent was applied, and then formed by curing by irradiation with a glass transition temperature of 50 to 200 ° C. An adhesive paper for copying provided with a radiation-polymerizable layer having the above has already been proposed (Japanese Patent Laid-Open No. 63-37356, Japanese Patent Publication No. 5-5352).

However, since the radiation-polymerized layer is often transparent, it is not always easy to confirm whether or not the radiation-polymerized layer is provided on the end surface of the adhesive paper for copying, and therefore, the end surface of the adhesive paper for copying is not necessarily confirmed. It is desired to be able to easily confirm whether or not the radiation-polymerized layer is provided in the.

An object of the present invention is to solve the above problems associated with the prior art, and since the adhesive does not stick out from the end face of the adhesive paper for copying, the photosensitive material of the copying machine is exposed. The body drum is not contaminated by the adhesive, and the organic solvent does not soak into the top paper or release paper to curl it. An object of the present invention is to provide a pressure-sensitive adhesive paper for copying, which allows easy and reliable confirmation of whether or not a preventable radiation-polymerizable layer is provided.

SUMMARY OF THE INVENTION An adhesive paper for copying according to the present invention is for copying in which an upper paper and a release paper are laminated so that an adhesive layer provided on a lower surface of the upper paper and a release surface of the release paper are in contact with each other. In the pressure-sensitive adhesive paper, a radiation-polymerized layer is provided on the end surface of the pressure-sensitive adhesive paper for copying, and the radiation-polymerized layer comprises (i) a dye and (ii) (a) a radiation-polymerizable prepolymer and (b) a molecule. A radiation-polymerizable composition comprising a radiation-polymerizable monomer having a radiation-polymerizable carbon-carbon double bond and containing no solvent, is applied to the end face of the pressure-sensitive adhesive paper for copying, and then the radiation-sensitive composition is applied. It is formed by curing by irradiation and is characterized by having a glass transition temperature of 50 to 200 ° C.

DETAILED DESCRIPTION OF THE INVENTION The adhesive paper for copying according to the present invention will be specifically described below.

As shown in FIG. 1, an adhesive paper 1 for copying according to the present invention has an upper paper 2 and a release paper 3, and an adhesive layer 4 provided on the lower surface of the upper paper and a release surface of the release paper 3. A radiation-polymerized layer 5 cured by irradiation with radiation is formed on at least one end surface of the pressure-sensitive adhesive paper 1 for copying, which is laminated so as to be in contact with each other.
Is provided.

The radiation-polymerizable layer 5 is formed by applying a radiation-polymerizable composition to the end surface of the pressure-sensitive adhesive paper 1 for copying and then irradiating the composition to cure the composition.

The radiation-polymerizable composition used for forming the radiation-polymerizable layer 5 contains (i) a dye and (ii) a radiation-polymerizable compound, and the (ii) radiation-polymerizable compound is
It contains (a) a radiation-polymerizable prepolymer and (b) a radiation-polymerizable monomer having a radiation-polymerizable carbon-carbon double bond in the molecule. Further, this radiation-polymerizable compound may contain (c) a polymerization initiator in addition to (a) and (b) above.

The “(i) dye” contained in the radiation-polymerizable composition as used herein means a pigment in addition to the so-called dye.

Specifically, in addition to colored dyes that are generally widely used as dyes, fluorescent dyes including fluorescent white dyes are used. Of these, fluorescent dyes that are colorless and transparent in the visible light region are particularly preferable. When the radiation-polymerizable composition contains a fluorescent dye that is colorless and transparent in the visible light region, a colorless and transparent radiation-polymerized layer can be provided on the end face of the pressure-sensitive adhesive paper for copying, and also for copying. Whether or not the radiation-polymerized layer is provided on the end surface of the pressure-sensitive adhesive paper can be easily confirmed by irradiating the end surface of the pressure-sensitive adhesive paper for copying with ultraviolet rays or the like, and it is possible to significantly simplify the production control. Become. On the other hand, when a colored dye or a pigment in the form of fine particles is contained in the radiation-polymerizable composition, since the colored radiation-polymerized layer is provided on the end surface of the pressure-sensitive adhesive paper for copying, the end surface of the pressure-sensitive adhesive paper for copying is simply visible. It can be easily confirmed whether or not the radiation-polymerized layer is provided.

Specific examples of the fluorescent dye include 2,5-bis (5-t-
Butylbenzoxazolyl (2)) thiophene, aromatic heterocyclic compounds, naphthalimide type fluorescent brightening dyes, 2-
Furyl- (3-p-anisoyl) chromene, diphenylchloromethyl-1,3,4-oxadiazole and the like can be used.

As the dye, specifically, a diphenylmethane dye, a triphenylmethane dye, a thiazole dye, a basic dye, a quinoline dye, a nitro dye, an acid dye or the like is used.

Further, as the pigment, an organic pigment or an inorganic pigment is used, specifically, an azo pigment copper phthalocyanine-based pigment,
A thioxazine pigment, a condensed azo pigment, a chromate pigment, a ferrocyanide pigment, a metal oxide pigment and the like are used.

Such (i) dye is added to the radiation-polymerizable composition in an amount of 0.00
It is desirable that it is contained in an amount of 5 to 2.0% by weight, preferably 0.01 to 1.0% by weight.

Specific examples of the (a) radiation-polymerizable prepolymer used as the (ii) radiation-polymerizable compound in the radiation-polymerizable composition include urethane acrylate-based oligomers. Polyether type polyol compounds or low molecular weight alkyds, silicone resins, epoxy resins and polyvalent isocyanate compounds such as 2,4-
Terminal isocyanate obtained by reacting with tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane 4,4-diisocyanate, etc. In the nato urethane prepolymer, a (meth) acrylate having a hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
It is obtained by reacting 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate and the like. This urethane acrylate oligomer has at least one carbon-carbon double bond.

It is desirable that the urethane acrylate-based oligomer has a molecular weight of about 500 to 10,000, preferably about 1,000 to 5,000.

In some cases, as the radiation-polymerizable prepolymer (a), a mixed prepolymer obtained by mixing a urethane acrylate oligomer with epoxy acrylate, polyester acrylate, silicone acrylate, or the like can also be used.

Such a urethane acrylate-based oligomer or a (a) radiation-polymerizable prepolymer obtained by adding an epoxy acrylate to the urethane acrylate-based oligomer is preferably used in an amount of 90 to 30% by weight in the radiation-polymerizable composition. .

The radiation-polymerizable monomer (b) used as the radiation-polymerizable compound (ii) in the radiation-polymerizable composition and having a radiation-polymerizable carbon-carbon double bond in the molecule is the radiation-polymerizable carbon-carbon double bond. A compound having at least two bonds is preferable, and specifically, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-
Examples thereof include butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, and commercially available oligoester acrylate.

Further, as the radiation-polymerizable monomer (b) having a radiation-polymerizable carbon-carbon double bond, radiation-polymerization such as N-vinyl-2-pyrrolidone, 2-ethylhexyl acrylate, nonylphenoxy polyethylene glycol acrylate or 2-hydroxyethyl acrylate. Sexual carbon −
A compound having one carbon double bond can also be used.

Such a radiation-polymerizable monomer (b) is preferably used in the radiation-polymerizable composition in an amount of 10 to 70% by weight.

A radiation-polymerizable composition comprising the compound having at least two radiation-polymerizable carbon-carbon double bonds as described above and the compound having one radiation-polymerizable carbon-carbon double bond as (b) a radiation-polymerizable monomer. When used inside, the glass transition temperature of the radiation-polymerized layer obtained is 50 to 200.
C., the flexibility is imparted, and the radiation-polymerized layer 5 is prevented from cracking and falling off when the pressure-sensitive adhesive paper for copying according to the present invention is brought into pressure contact with the photosensitive drum of a copying machine.

Further, in the present invention, the (c) polymerization initiator is used in the radiation-polymerizable compound. As such a polymerization initiator, a radical-generating type polymerization initiator or an ionic polymerization type initiator can be used.

As the radical-generating type polymerization initiator, specifically, 2,2
-Diethoxyacetophenone, benzophenone, 4,4-
Benzophenone compounds such as bisdimethylaminobenzophenone, benzyl, dibenzoyl, benzoin methyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin ether compounds, acetophenone compounds or azo compounds can be used.

Further, as the ionic polymerization type polymerization initiator, specifically,
Acids, alkali metals, metal alkyls and the like can be used.

Such (c) polymerization initiator is preferably used in the radiation-polymerizable composition in an amount of 1 to 10% by weight.

Further, in the present invention, the sensitizer (d) can be used in the radiation-polymerizable compound, if necessary. As such a sensitizer (d), amines such as triethylamine, diethylaminoethyl methacrylate and triethylenetetramine, urea compounds, sulfur compounds, nitrile compounds, phosphorus compounds, chlorine compounds and the like are used.

Such a (d) sensitizer is contained in the radiation-polymerizable composition in an amount of 0.
It is preferably used in an amount of -10% by weight.

Furthermore, in the present invention, the stabilizer (e) can be used in the radiation-polymerizable compound, if necessary. As such a stabilizer (e), quaternary ammonium chloride, hydroquinone, diethylhydroxyamine, benzothiazole, hydroquinone monomethyl ether and the like can be used.

Such a (e) stabilizer is a radiation-polymerizable compound,
It is preferably used in an amount of 0 to 2% by weight.

In the present invention, a radiation-polymerizable composition containing each component as described above is applied to the end surface of a pressure-sensitive adhesive copy paper, and then cured by irradiation with radiation to form a radiation-polymerized layer on the end surface of the pressure-sensitive adhesive copy paper. However, this radiation-polymerized layer is
50-200 ℃, preferably 70-150 ℃, more preferably 80
It has a glass transition temperature of ~ 130 ° C. If the glass transition temperature of the radiation-polymerized layer exceeds 200 ° C., the radiation-polymerized layer may break and fall off when the pressure-sensitive adhesive paper for copying is fed into the copying machine and brought into pressure contact with the photosensitive drum. On the other hand, when the glass transition temperature is lower than 50 ° C., when a pressure-sensitive adhesive paper for copying is laminated, a blocking phenomenon of the end face occurs and the effect of preventing the adhesive from sticking out by the radiation-polymerized layer is lost, which is not preferable.

Next, a method of manufacturing the adhesive paper for copying according to the present invention will be described.

The top paper 2 and the release paper 3 are laminated so that the pressure-sensitive adhesive layer 4 provided on the lower surface of the top paper and the release surface of the release paper 3 are in contact with each other,
Next, the radiation-polymerizable composition containing each component as described above is applied to at least one end surface of the obtained laminate.

To apply the radiation-polymerizable composition to the end surface of the laminate, when the pressure-sensitive adhesive paper for copying is in the form of a roll, the composition may be applied to the end surface by brush coating, spraying, silk-screening, or the like. Alternatively, or in the sheet cutting line, the pressure-sensitive adhesive paper for roll copying may be continuously applied to the end faces before sheet cutting.

In addition, a smoothing operation of contacting the end surface of the pressure-sensitive adhesive paper for copying having the radiation-polymerizable composition applied to the end surface with a felt or sponge containing the radiation-polymerizable composition,
Addition to the end face is preferable because the radiation-polymerizable composition can be uniformly applied to the end face of the pressure-sensitive adhesive paper for copying.

Then, the end face of this adhesive paper for copying is irradiated with ultraviolet rays (UV) or electron beams (EB) to remove (a) the radiation-polymerizable prepolymer and (b) the radiation-polymerizable monomer contained in the radiation-polymerizable composition. It may be polymerized and cured.

After the radiation-polymerized layer is thus provided on the end surface of the pressure-sensitive adhesive paper for copying, whether or not the radiation-polymerized layer is surely provided is (i) when a fluorescent dye is used as the dye,
It can be surely confirmed by irradiating the end surface of the adhesive paper for copying with ultraviolet rays. Further, when a colored dye or a pigment is used as the dye (i), the radiation-polymerized layer is colored, so that it can be easily confirmed simply by visual inspection.

Effect of the Invention The pressure-sensitive adhesive paper for copying according to the present invention is provided with a radiation-polymerizable composition formed by coating a radiation-polymerizable composition comprising specific components on at least one end face and curing the composition by radiation irradiation. Since the radiation-polymerized layer has a specific glass transition temperature, it is possible to prevent the adhesive from squeezing out from the end surface of the pressure-sensitive adhesive paper for copying, and to prevent the radiation-polymerized layer from cracking and falling off. The body drum etc. are not contaminated by the adhesive. Moreover, since the radiation-polymerizable composition does not include an organic solvent or water, it is not necessary to dry the top paper of the adhesive paper, the release paper, and the top paper and the release paper do not curl due to being coated, Since the upper radiation-polymerizable composition is cured not by heating but by irradiating with radiation, the adhesive paper for copying is not heated to a high temperature, and therefore the upper paper and the release paper do not curl. In addition, it is possible to easily confirm whether or not the radiation-polymerized layer is provided on the end surface of the pressure-sensitive adhesive paper for copying.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 100 parts by weight of a urethane acrylate oligomer having a weight average molecular weight (polystyrene conversion) of 4,000, 5 parts by weight of trimethylolpropane triacrylate, 0.2 parts by weight of benzyl dimethyl ketal, and a fluorescent dye (2,5-bis (5 −
t-butylbenzoxazolyl (2)) thiophene) 0.02
A radiation-polymerizable composition is prepared by mixing with a part by weight, and this is applied to the end surface of a copying pressure-sensitive adhesive paper in which a top paper and a release paper are laminated via an acrylic pressure-sensitive adhesive. Smoothing operation was carried out by contacting with felt, and then this end face was irradiated with an 800 W high-pressure mercury lamp from an irradiation distance of 3 cm for about 1 second to produce a pressure-sensitive adhesive paper for copying having a radiation-polymerized layer formed on the end face.

The glass transition temperature of the radiation-polymerized layer thus formed was 150 ° C.

Make a copy with a copier using this adhesive paper for copying,
The adhesive property, curl property, running property, image property, and the presence or absence of contamination of the photosensitive drum by the adhesive were examined. The running property, the image property, and the presence or absence of contamination of the photosensitive drum by the adhesive were examined using 200 sheets of the copying adhesive paper.
The presence or absence of contamination of the photosensitive drum is indicated by the presence or absence of black dots appearing on the copy paper.

In addition, whether or not the radiation-polymerized layer was provided on the end surface of the copying adhesive paper in this manner was determined by irradiating the end surface of this copying adhesive paper with ultraviolet rays of 375 to 380 nm.
This judgment operation was extremely easy.

The results are shown in Tables 1 and 2.

Example 2 100 parts by weight of a urethane acrylate oligomer having a weight average molecular weight (converted to polystyrene) of 3,800, 10 parts by weight of trimethylolpropane triacrylate, 1 part by weight of benzyl dimethyl ketal, and a fluorescent dye (aromatic heterocyclic fluorescent). Dye) 0.5 part by weight was mixed to prepare a radiation-polymerizable composition.

Using this radiation-polymerizable composition, a pressure-sensitive adhesive paper for copying was manufactured in the same manner as in Example 1, and the characteristics were examined in the same manner as in Example 1 using this pressure-sensitive adhesive paper for copying.

The results are shown in Tables 1 and 2.

Example 3 In the same manner as in Example 1 except that 0.1 part by weight of Solvent Red-27 was used in place of the fluorescent dye, a pressure-sensitive adhesive copying paper having a radiation-polymerized layer formed on the end face was produced. did.

Whether or not the radiation-polymerized layer was provided on the end surface of the pressure-sensitive adhesive paper for copying thus obtained could be easily confirmed only by visual inspection.

Example 4 An adhesive paper for copying having a radiation-polymerized layer formed on the end face was produced in the same manner as in Example 1 except that 0.05 part by weight of the phthalocyanine pigment was used instead of the fluorescent dye.

Whether or not the radiation-polymerized layer was provided on the end surface of the pressure-sensitive adhesive paper for copying thus obtained could be easily confirmed only by visual inspection.

Comparative Example 1 A pressure-sensitive adhesive paper for copying was produced in the same manner as in Example 2 except that the fluorescent dye was not used in the radiation-polymerizable composition. The characteristics were examined in the same manner as in No. 1.

The results are shown in Tables 1 and 2.

Comparative Example 2 In Example 1, copying was performed by a copying machine in the same manner as in Example 1 except that the radiation polymerization layer was not formed on the end surface of the pressure-sensitive adhesive paper for copying, and various characteristics were examined.

The results are shown in Tables 1 and 2.

From Example 1, Example 2, Comparative Example 1, and Comparative Example 2, by forming a radiation-polymerized layer having a specific glass transition temperature on the end surface of the pressure-sensitive adhesive paper for copying, contamination of the photosensitive drum can be prevented. I understand.

Further, by including a dye, particularly a fluorescent dye, in the radiation-polymerizable layer, it can be easily determined whether or not the radiation-polymerized layer is formed on the end surface of the pressure-sensitive adhesive paper for copying.

[Brief description of drawings]

FIG. 1 is a sectional view of an adhesive paper for copying according to the present invention. 1 ... Adhesive paper for copying, 2 ... Top paper 3 ... Release paper, 4 ... Adhesive layer 5 ... Radiation polymerization layer

Claims (9)

[Claims] 1. A copier adhesive paper comprising a top paper and a release paper laminated such that an adhesive layer provided on a lower surface of the top paper and a release surface of the release paper are in contact with each other. A radiation-polymerizable layer is provided on the end face of the, and the radiation-polymerizable layer comprises (i) a dye and (ii) (a) a radiation-polymerizable prepolymer and (b) a radiation-polymerizable carbon-carbon double molecule in the molecule. A radiation-polymerizable composition comprising a radiation-polymerizable monomer having a bond and containing no solvent, is applied to at least one end face of a pressure-sensitive adhesive paper for copying, and then cured by irradiation with radiation. A pressure-sensitive adhesive paper for copying, which is formed and has a glass transition temperature of 50 to 200 ° C. 2. The adhesive paper for copying according to claim 1, wherein the dye is a fluorescent dye. 3. The pressure-sensitive adhesive paper for copying according to claim 1, wherein the radiation-polymerizable prepolymer is (a-1) a urethane acrylate oligomer. 4. A copy according to claim 1, wherein the radiation-polymerizable prepolymer comprises (a-1) a urethane acrylate oligomer and (a-2) a polyester acrylate, an epoxy acrylate or a silicone acrylate. Adhesive paper. 5. The radiation-polymerizable monomer having a radiation-polymerizable carbon-carbon double bond in the molecule is trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol. Monohydroxypentaacrylate,
Dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, N-vinyl 1-2-pyrrolidone, 2-ethylhexyl acrylate, nonylphenoxy polyethylene The adhesive paper for copying according to claim 1, which is glycol acrylate or 2-hydroxyethyl acrylate. 6. The pressure-sensitive adhesive paper for copying according to claim 1, wherein the radiation-polymerizable composition further comprises (c) a polymerization initiator. 7. The polymerization initiator (c) is 2,2-diethoxyacetophenone, benzophenone, 4,4-bisdimethylaminobenzophenone, dibenzoyl, benzoin methyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone or azo. The pressure-sensitive adhesive paper for copying according to claim 6, which is a compound. 8. The adhesive paper for copying according to claim 1, wherein the radiation-polymerized layer has a glass transition temperature of 70 to 150 ° C. 9. The pressure-sensitive adhesive paper for copying according to claim 1, wherein the radiation-polymerized layer has a glass transition temperature of 80 to 130 ° C.