JP2006282721A - Method for producing colored sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a colored sheet, by which the colored sheet in which a pigment is dispersed in excellent dispersibility can be produced. <P>SOLUTION: This method for producing the colored sheet colored with a resin liquid containing the pigment is characterized by comprising the following processes (A) to (B). The process (A): a process for mixing the pigment with at least one dispersant selected from alkylsulfosuccinates, polyoxyethylene alkyl ether phosphates and sorbitan fatty acid esters and a diluent to prepare the pigment dispersion. The process (B): a process for compounding the pigment dispersion with the resin liquid to prepare the pigment-containing resin liquid. The resin liquid is preferably a solvent-free resin liquid substantially containing no organic solvent. The liquid component of the resin liquid is preferably a liquid component containing at least the monomer component of a photocurable resin or a thermosetting resin or a partial polymer thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing colored sheets.

  As a method for producing colored sheets (colored sheets), a method of mixing a pigment into a material solution of the sheet is common. For example, colored pressure-sensitive adhesive sheets (colored pressure-sensitive adhesive sheets) can be obtained by mixing a pigment into a pressure-sensitive adhesive solution as a material and forming a sheet (see Patent Documents 1 and 2).

JP-A-10-130591 JP 2003-155318 A

  In such a method for producing colored sheets, the pigment is often present in a large granular form due to poor dispersibility of the pigment, which causes a problem that coloring is often non-uniform, which is a problem. In contrast, pigment manufacturing companies have developed processed pigments that can be well dispersed in various material solutions (such as pressure-sensitive adhesive solutions) when manufacturing colored sheets (such as colored adhesive sheets). The compatibility and dispersion stability of pigments are improved.

  Conventionally, as a material solution, for example, when an adhesive solution is taken as an example, a solvent using a solvent such as toluene or ethyl acetate is generally used. In many cases, the compatibility was good. However, due to environmental problems in recent years, the use of a material composition that does not contain a solvent is increasing. An example of such a material composition that does not contain a solvent is a curable pressure-sensitive adhesive such as a photo-curable acrylic pressure-sensitive adhesive. The main component of the photo-curing acrylic pressure-sensitive adhesive is an acrylic monomer such as (meth) acrylic acid alkyl ester, and is less compatible with the processed pigment than the solvent. Therefore, when the processed pigment is mixed with the photocurable acrylic pressure-sensitive adhesive in the same manner as in the case of the solvent-type acrylic pressure-sensitive adhesive, there is a problem that the pigment is poorly dispersed.

Accordingly, an object of the present invention is to provide a method for producing colored sheets, which can produce colored sheets in which pigments are dispersed with excellent dispersibility.
Another object of the present invention is to provide a colored sheet having excellent colorability by dispersing a pigment in a solventless resin liquid with excellent dispersibility even when using a solventless resin liquid. It is in providing the manufacturing method of the colored sheets which can manufacture a kind.

  As a result of intensive studies to achieve the above object, the present inventors have formulated a pigment into a resin liquid by using a pigment dispersion containing a pigment, a specific dispersant, and a diluent. It has been found that it is possible to produce a colored sheet that can be dispersed with excellent dispersibility and colored with excellent colorability. The present invention has been completed based on these findings.

That is, the present invention is a method for producing colored sheets using a resin liquid containing a pigment, which comprises the following steps (A) to (B). Provide a method.
Step (A): A pigment dispersion is prepared by mixing a pigment, at least one dispersant selected from alkyl sulfosuccinate, polyoxyethylene alkyl ether phosphate ester salt and sorbitan fatty acid ester, and a diluent. Step (B): Step of preparing the resin liquid containing the pigment by blending the pigment dispersion into the resin liquid

  The resin liquid may be a solventless resin liquid that does not substantially contain an organic solvent. The liquid component of the resin liquid is preferably a liquid component containing at least a monomer component of a photocurable resin or a thermosetting resin or a partial polymer thereof. As the monomer component of such a photocurable resin or thermosetting resin, an acrylic monomer component is suitable.

  The pigment preferably contains at least carbon black. As the pigment, a pigment composition in which the pigment is dispersed in the resin component can be used. Further, the diluent preferably contains at least the same liquid component as the main component of the liquid component in the resin liquid.

  In such a pigment dispersion, the ratio of the dispersant is preferably 1 to 50% by weight with respect to the total amount of the pigment, and the ratio of the diluent is pigment: diluent (weight ratio) = 1: 99-80. : A ratio of 20 is preferable.

  The colored sheets of the present invention may be colored adhesive sheets. As the colored pressure-sensitive adhesive sheet, a colored pressure-sensitive adhesive sheet having a configuration formed only from the colored pressure-sensitive adhesive layer can be suitably used.

  According to the method for producing colored sheets of the present invention, it is possible to produce colored sheets in which pigments are dispersed with excellent dispersibility. Moreover, even if a solventless resin liquid is used, the pigment can be dispersed in the solventless resin liquid with excellent dispersibility to produce colored sheets having excellent colorability. it can.

In the manufacturing method of the colored sheets of this invention, the colored sheets are manufactured using the resin liquid containing a pigment through the following process (A)-(B).
Step (A): A pigment dispersion is prepared by mixing a pigment, at least one dispersant selected from alkyl sulfosuccinate, polyoxyethylene alkyl ether phosphate ester salt and sorbitan fatty acid ester, and a diluent. Process (pigment dispersion preparation process)
Step (B): A step of preparing a resin liquid containing a pigment (pigment-containing resin liquid) by blending the pigment dispersion into the resin liquid (pigment-containing resin liquid preparation step)

[Step (A)]
In step (A) (pigment dispersion preparation step), a pigment is mixed with at least one dispersant selected from alkyl sulfosuccinate, polyoxyethylene alkyl ether phosphate ester salt and sorbitan fatty acid ester, and a diluent. Thus, a pigment dispersion is prepared. Thus, in the pigment dispersion preparation step, when the pigment is dispersed, the specific dispersant and the diluent are used. Therefore, the pigment dispersion in which the pigment is dispersed can be easily prepared.

(Pigment)
The pigment is not particularly limited, and may be an inorganic pigment or an organic pigment. The pigments can be used alone or in combination of two or more. Specifically, examples of the pigment include black pigments such as carbon black, titanium black, and black iron oxide; white pigments such as titanium oxide, zinc white, calcium carbonate, barium sulfate, and clay; and aluminum powder (silver) , Bronze powder (gold), Bengala (red), ultramarine blue (blue), bitumen (blue), yellow iron oxide (yellow), copper phthalocyanine (blue), halogenated copper phthalocyanine (green), diketopyrrolopyrrole (red) , Condensed azo (red, brown), quinacridone (red, purple), isoindolinone (yellow), diarylide (yellow), anthraquinone (yellow), and the like. In addition, as the pigment, a pigment composition in which the pigment is dispersed in the resin component by kneading one or more pigments as exemplified above in a resin component such as a rosin ester resin. Products (so-called “processed pigments”) can also be used.

  In the present invention, as the pigment, a pigment containing at least carbon black can be preferably used, and carbon black is particularly preferable. By using a black pigment such as carbon black as the pigment, black colored sheets colored black can be produced.

(Dispersant)
In the present invention, as the dispersant, at least one dispersant selected from alkyl sulfosuccinate, polyoxyethylene alkyl ether phosphate ester salt and sorbitan fatty acid ester is used. The alkylsulfosuccinate may be a monoalkylsulfosuccinate, but a dialkylsulfosuccinate can be suitably used. In the alkylsulfosuccinate such as monoalkylsulfosuccinate and dialkylsulfosuccinate, the alkyl group is not particularly limited, but is preferably an alkyl group having 3 to 20 carbon atoms, and more preferably an alkyl group having 6 to 18 carbon atoms. is there. Specifically, as the alkyl group, for example, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, A heptadecyl group, an octadecyl group, etc. are mentioned. The two alkyl groups in the dialkylsulfosuccinate may be different but are preferably the same. In the alkylsulfosuccinate, examples of the cation forming the salt include alkali metal ions (sodium ion, potassium ion, etc.) and ammonium ions, and alkali metal ions are preferable, and sodium ions are particularly preferable. It is. Therefore, the alkylsulfosuccinate can have a salt form such as an alkali metal salt (sodium salt, potassium salt, etc.) or an ammonium salt.

  Specifically, as the alkylsulfosuccinate, for example, di (octadecyl) sodium salt of sulfosuccinic acid, di (heptadecyl) sodium salt of sulfosuccinic acid, di (hexadecyl) sodium salt of sulfosuccinic acid, di (pentadecyl) sodium salt of sulfosuccinic acid, Sulfosuccinic acid di (tetradecyl) sodium salt, Sulfosuccinic acid di (tridecyl) sodium salt, Sulfosuccinic acid di (dodecyl) sodium salt, Sulfosuccinic acid di (decyl) sodium salt, Sulfosuccinic acid di (nonyl) sodium salt, Sulfosuccinic acid di (octyl) ) Sodium salt, di (2-ethylhexyl) sodium sulfosuccinate, di (heptyl) sodium sulfosuccinate, di (hexyl) sodium sulfosuccinate, and the like.

  In the present invention, it is also possible to use a cycloalkylsulfosuccinate (for example, cyclohexylsulfosuccinate) instead of the alkylsulfosuccinate.

  The polyoxyethylene alkyl ether phosphate ester salt has a form in which one or two alkyl-oxy-poly (ethyleneoxy) groups are bonded to the phosphorus atom of the phosphate and become a salt. . Accordingly, the polyoxyethylene alkyl ether phosphate ester salt includes mono (polyoxyethylene alkyl ether) phosphate ester salt and di (polyoxyethylene alkyl ether) phosphate ester salt. In such an alkyl-oxy-poly (ethyleneoxy) group [ie, polyoxyethylene alkyl ether moiety], the number of ethyleneoxy repeats related to the poly (ethyleneoxy) moiety is not particularly limited. It can be suitably selected from the range of (preferably 3 to 20). The alkyl group is not particularly limited, but for example, an alkyl group having 6 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 (particularly 10 to 18) is particularly preferable. Specifically, examples of the alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. When the polyoxyethylene alkyl ether phosphate ester salt has two alkyl-oxy-poly (ethyleneoxy) groups, the two alkyl groups may be different but the same. Is preferred. Furthermore, in the polyoxyethylene alkyl ether phosphate ester salt, examples of the cation forming the salt include alkali metal ions (sodium ion, potassium ion, etc.) and ammonium ions, and alkali metal ions are preferred. In particular, sodium ion is preferred. Therefore, the polyoxyethylene alkyl ether phosphate ester salt can have a form of a salt such as an alkali metal salt (sodium salt, potassium salt, etc.) or an ammonium salt.

  Specifically, as polyoxyethylene alkyl ether phosphate ester salt, for example, (mono or di) (polyoxyethylene decyl ether) phosphate ester sodium salt, (mono or di) (polyoxyethylene undecyl ether) Phosphate ester sodium salt, (mono or di) (polyoxyethylene dodecyl ether) phosphate sodium salt, (mono or di) (polyoxyethylene tridecyl ether) phosphate sodium salt, (mono or di) (poly Oxyethylene tetradecyl ether) phosphate sodium salt, (mono or di) (polyoxyethylene pentadecyl ether) phosphate sodium salt, (mono or di) (polyoxyethylene hexadecyl ether) phosphate sodium salt, (Mono or di (Polyoxyethylene heptadecyl ether) phosphoric acid ester sodium salt, and the like (mono or di) (polyoxyethylene octadecyl ether) phosphate ester sodium salt.

  In the present invention, instead of polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl aryl ether phosphate ester salt (for example, polyoxyethylene alkylphenyl ether phosphate ester salt) or alkyl phosphate ester It is also possible to use a salt.

  Sorbitan fatty acid ester is a reaction product of sorbitan and / or sorbitol and fatty acid, and generally has monoester form, diester form, triester form, tetraester form, etc. It may have a higher ester form. In the sorbitan fatty acid ester, the fatty acid used as a raw material is not particularly limited. For example, a fatty acid having 6 to 30 carbon atoms (preferably 6 to 22, more preferably 8 to 18) can be used. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid. The fatty acid may be a linear fatty acid or a branched fatty acid. Fatty acids can be used alone or in combination of two or more. Specifically, as the fatty acid, for example, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecane Examples include acids (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), isostearic acid, oleic acid, behenic acid, coconut fatty acid, and beef tallow fatty acid. As the fatty acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid and oleic acid are suitable.

  Specifically, as the sorbitan fatty acid ester, for example, sorbitan (mono or tri) dodecanoic acid ester, sorbitan (mono or tri) tridecanoic acid ester, sorbitan (mono or tri) tetradecanoic acid ester, sorbitan (mono or tri) pentadecane Examples include acid esters, sorbitan (mono or tri) hexadecanoate, sorbitan (mono or tri) heptadecanoate, sorbitan (mono or tri) octadecanoate, sorbitan (mono or tri) oleate, and the like.

  Such a dispersant mainly has a role for making the pigment compatible with the resin liquid. Note that these dispersants can also belong to a lubricant that improves wettability.

  The amount of the dispersant used is not particularly limited. For example, it may be selected from the range of 1 to 50% by weight (preferably 3 to 40% by weight, more preferably 5 to 30% by weight) with respect to the total amount of the pigment. it can. In addition, when the proportion of the dispersant is less than 1% by weight with respect to the total amount of the pigment, the dispersibility of the pigment in the resin liquid is lowered. On the other hand, when the proportion exceeds 50% by weight, the adhesive property is lowered. There is.

(Diluent)
As a diluent, it becomes a main liquid of a pigment dispersion liquid, and can be arbitrarily selected and used. The diluent may be composed of only one component, or may be composed of two or more components. Since the diluent is used to dilute the pigment, the pigment and the diluent are preferably a combination having compatibility. Therefore, for example, a combination of a pigment insoluble in water and water as a diluent is not appropriate and is not preferred. Therefore, it is important to select the diluent as appropriate according to the compatibility with the pigment.

  Further, from the viewpoint of preparing the resin liquid containing the pigment by blending the pigment dispersion into the resin liquid, the diluent may be a diluent containing at least the same liquid component as the liquid component in the resin liquid. desirable. Thus, when a diluent containing at least the same liquid component as the liquid component in the resin liquid is used as the diluent, the diluent can be easily incorporated into the resin liquid when the pigment dispersion is blended into the resin liquid. It is also possible to prepare a pigment-containing resin liquid that can be mixed and does not contain unnecessary components.

  In the present invention, as a diluent, a diluent containing at least the same liquid component as the main component (liquid main component) of the liquid component in the resin liquid (particularly dilution with the same liquid component as the liquid main component in the resin liquid). Agent) can be preferably used. As described above, when the same liquid component as the liquid main component in the resin liquid is used as the diluent, the amount of the liquid main component in the resin liquid is used as the diluent from a predetermined amount or a necessary amount. It may be an amount obtained by reducing the amount of the liquid component. That is, in the present invention, a part of the liquid main component in the resin liquid can be used as a diluent for the pigment dispersion.

  Therefore, when the liquid main component in the resin liquid is, for example, an acrylic monomer component (for example, 2-ethylhexyl acrylate), the diluent is the same as the acrylic monomer component that is the liquid main component in the resin liquid. An acrylic monomer component can be used.

  The amount of the diluent used is not particularly limited. However, if the ratio of the diluent to the pigment is too small (that is, the ratio of the pigment to the diluent is too large), it is difficult to obtain uniform compatibility. It is desirable that the amount is moderate. Specifically, the amount of diluent used is, for example, pigment: diluent (weight ratio) = 1: 99 to 80:20 (preferably 1:99 to 50:50, more preferably 1:99 to 30). : 70) can be selected from the range of the ratio.

(Method for preparing pigment dispersion)
In the pigment dispersion preparation step, as described above, the pigment dispersion is prepared by mixing the pigment, the predetermined dispersant, and the diluent. In preparing the pigment dispersion, the method of mixing the pigment, the dispersant, and the diluent is not particularly limited. For example, the method of adding the pigment and the dispersant to the diluent while stirring is mixed. , A method in which a dispersant is added to and mixed with a diluent under stirring, and a method in which a pigment is added and mixed. Any mixing method may be used. In addition, as a charging method when adding a pigment or a dispersant to the diluent, for example, a batch charging method, a split charging method (a continuous charging method, an intermittent charging method, etc.) Etc.

  In the present invention, the temperature at which the pigment dispersion is prepared is not particularly limited and is usually room temperature, but may be higher or lower than room temperature.

[Step (B)]
In the step (B) (pigment-containing resin liquid preparation step), the pigment-containing resin liquid is prepared by blending the pigment dispersion obtained in the step (A) (pigment dispersion liquid preparation step) with the resin liquid. . Thus, in the pigment-containing resin liquid preparation step, the pigment dispersion liquid obtained by the pigment dispersion preparation step is used when the pigment is blended into the resin liquid, so that the pigment is excellent in the resin liquid. It can be blended with dispersibility.

(Resin liquid)
The resin liquid is not particularly limited as long as it is a liquid containing the resin component in the colored sheets. The resin liquid may be, for example, a resin liquid in which one or two or more resin components (such as a thermoplastic resin component) are dissolved in an organic solvent (such as toluene or ethyl acetate). From the viewpoint of environmental problems, a solventless resin liquid (solventless resin liquid) that does not substantially contain an organic solvent is preferable. Examples of the solventless resin liquid include a resin liquid obtained from a photocurable resin composition containing at least a monomer component of a photocurable resin or a partial polymer thereof (photocurable resin component), and a monomer of a thermosetting resin. The resin liquid by the thermosetting resin composition which contains at least a component or its partial polymer (thermosetting resin component) etc. are mentioned. That is, examples of the solventless resin liquid include a resin liquid in which a liquid component is a liquid component containing at least a monomer component of a photocurable resin or a thermosetting resin or a partial polymer thereof. Such a solventless resin liquid is a resin liquid for producing colored sheets made of a photo-curable resin or a thermosetting resin, and a monomer component as a liquid component and / or a partial polymer thereof, and necessary The resin composition (photocurable resin composition or thermosetting resin composition) containing a polymerization initiator or the like that initiates polymerization by light irradiation or heating according to the above. In the present invention, as the solventless resin liquid, a resin liquid based on a photocurable resin composition can be suitably used.

  The photocurable resin composition may be, for example, a photocurable resin composition including a monomer mixture obtained by mixing a monomer component and, if necessary, a photopolymerization initiator, After mixing the monomer component and photopolymerization initiator, if necessary, photo-curability including a partial polymer of the monomer obtained by polymerizing only a part of the monomer component by irradiation with light It may be a resin composition (syrup).

  In addition, when the colored sheets are pressure-sensitive adhesive sheets (colored pressure-sensitive adhesive sheets) having a colored pressure-sensitive adhesive layer, a pressure-sensitive adhesive solution (pressure-sensitive adhesive composition) can be used as the resin liquid. In particular, when the resin liquid is a solvent-free resin liquid, the solvent-free resin liquid is a photocurable pressure-sensitive adhesive composition or a thermosetting pressure-sensitive adhesive composition (preferably a photocurable pressure-sensitive adhesive composition). Can be used.

  In the solvent-free resin liquid, the monomer component in the photocurable resin component or the thermosetting resin component is not particularly limited. For example, known light such as an acrylic monomer component, a polyester monomer component, and an epoxy monomer component. It can select suitably from the monomer component of curable resin or a thermosetting resin, and can use it. Therefore, for example, when the solventless resin liquid is a photocurable adhesive composition, the solventless resin liquid includes a photocurable acrylic adhesive, a photocurable polyester adhesive, and a photocurable epoxy system. An adhesive can be used. For example, when the solventless resin liquid is a thermosetting pressure-sensitive adhesive composition, the solventless resin liquid includes a thermosetting acrylic pressure-sensitive adhesive, a thermosetting polyester pressure-sensitive adhesive, and a thermosetting epoxy type. An adhesive can be used.

  As such a monomer component, an acrylic monomer component can be suitably used. As the acrylic monomer component, for example, (meth) acrylic acid ester (meaning acrylic acid ester or methacrylic acid ester) can be used, and among them, (meth) acrylic acid alkyl ester is preferably used. be able to. In addition, only 1 type may be used for acrylic monomer components, such as (meth) acrylic acid ester, and 2 or more types may be used in combination.

Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate, ( T) Decyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, (meta ) (Meth) acrylic acid C _1-20 alkyl ester such as eicosyl acrylate [preferably (meth) acrylic acid C _2-14 alkyl ester, more preferably (meth) acrylic acid C _2-10 alkyl ester] and the like. It is done.

  Moreover, as (meth) acrylic acid ester other than (meth) acrylic acid alkyl ester, for example, it has an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate ( And (meth) acrylic acid ester and (meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate.

  In addition, (meth) acrylic acid ester is used as a main component of a monomer component. Therefore, it is important that the ratio of (meth) acrylic acid ester [particularly (meth) acrylic acid alkyl ester] is, for example, 50% by weight or more, preferably 70% by weight or more ( More preferably, it is 80% by weight or more.

  In addition, various copolymerizable monomers (ethylenically unsaturated monomers) such as polar group-containing monomers and polyfunctional monomers that can be copolymerized with acrylic monomer components are used as monomer components. It may be done. By using a copolymerizable monomer as the monomer component, for example, when the resin liquid is a pressure-sensitive adhesive composition (such as a photocurable acrylic pressure-sensitive adhesive composition), the adhesion to the adherend is improved. Or the cohesive strength of the pressure-sensitive adhesive can be increased. In addition, a copolymerizable monomer can be used individually or in combination of 2 or more types.

  As the polar group-containing monomer, a monoethylenically unsaturated monomer having a polar group can be suitably used. Specifically, examples of the polar group-containing monomer include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid, or anhydrides thereof (anhydrous anhydride). Maleic acid etc.); hydroxyl-containing monomers such as (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic acid hydroxyalkyl such as hydroxybutyl acrylate; acrylamide, methacrylamide, Amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; amino (meth) acrylate Ethyl, dimethylaminoethyl (meth) acrylate, (meth Amino group-containing monomers such as t-butylaminoethyl acrylate; glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N- Examples thereof include heterocyclic-containing vinyl monomers such as vinylimidazole and N-vinyloxazole. As the polar group-containing monomer, a carboxyl group-containing monomer such as acrylic acid or an anhydride thereof is suitable.

  The amount of the polar group-containing monomer used is desirably 30% by weight or less (for example, 1 to 30% by weight, preferably 3 to 20% by weight) based on the total amount of the monomer components. When the use amount of the polar group-containing monomer exceeds 30% by weight with respect to the total amount of the monomer components, for example, when the resin liquid is an adhesive composition (such as a photocurable acrylic adhesive composition), The cohesive force of the agent becomes too high, and the pressure-sensitive adhesiveness may be lowered. In addition, when there is too little usage-amount of a polar group containing monomer (for example, it is less than 1 weight% with respect to the monomer component whole quantity), for example, the cohesive force of an adhesive will fall and a high shear force will be obtained. Disappear.

  Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol di (meth). ) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) Acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hexyl di (meth) acrylate Such as theft and the like. Such a polyfunctional monomer can also be used as a cross-linking agent as shown below.

  The amount of the polyfunctional monomer used is 0.5% by weight or less (for example, 0.01 to 0.5% by weight, preferably 0.02 to 0.3% by weight) based on the total amount of the monomer components. It is desirable to be. When the amount of the polyfunctional monomer used exceeds 0.5% by weight relative to the total amount of the monomer components, for example, when the resin liquid is a pressure-sensitive adhesive composition (such as a photocurable acrylic pressure-sensitive adhesive composition). In some cases, the crosslink density becomes high and a necessary peeling force cannot be obtained. In addition, when there is too little usage-amount of a polyfunctional monomer (for example, it is less than 0.01 weight% with respect to the monomer component whole quantity), for example, the cohesion force of an adhesive will fall.

  Examples of copolymerizable monomers other than polar group-containing monomers and polyfunctional monomers include vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene. Olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; 2-methacryloyloxyethyl Isocyanate group-containing monomers such as isocyanate; fluorine-containing (meth) acrylate; and a silicon atom-containing (meth) acrylate.

  In a solventless resin liquid having a liquid component containing at least a monomer component of a photocurable resin or a thermosetting resin or a partial polymer thereof, as described above, by light irradiation or heating as necessary. A polymerization initiator for initiating polymerization can be used, and in particular, a polymerization initiator (photopolymerization initiator) by light irradiation can be suitably used. The photopolymerization initiator is not particularly limited, for example, acetophenone photopolymerization initiator, ketal photopolymerization initiator, benzoin ether photopolymerization initiator, benzophenone photopolymerization initiator, benzoin photopolymerization initiator, A benzyl photopolymerization initiator, an α-ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, a photoactive oxime photopolymerization initiator, a thioxanthone photopolymerization initiator, or the like can be used.

  Specifically, examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals, Inc.), 2,2-diethoxyacetophenone, 2,2- Examples include dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4-t-butyl-dichloroacetophenone. Examples of the ketal photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by Ciba Specialty Chemicals, Inc.), benzyldimethyl ketal, benzyl diethyl ketal Etc. Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisole. Examples include methyl ether.

  Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzyl photopolymerization initiator include benzyl.

  Furthermore, examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane- 1-one etc. are mentioned. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.

  Furthermore, examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like are included.

  Examples of other photopolymerization initiators include halogenated ketones and acylphosphine oxides (trade name “Lucirin TPO” manufactured by BASF, etc.).

  The amount of the photopolymerization initiator used is not particularly limited. However, if it is too large, a low molecular weight polymer (copolymer) is likely to be formed. On the other hand, if it is too small, the polymerization reaction is difficult to proceed. For example, 0.01 to 2 parts by weight (preferably 0.05 to 100 parts by weight of all monomer components [particularly all monomer components having (meth) acrylic acid ester as an acrylic monomer component as the main monomer component)] It is desirable to select appropriately from the range of ˜1 part by weight.

  In the activation of the photopolymerization initiator, light (particularly, active energy ray) can be used. In such light, examples of the active energy ray include ionizing radiation such as α rays, β rays, γ rays, neutron rays, electron rays, and ultraviolet rays, and ultraviolet rays are particularly preferable. The irradiation energy of light such as active energy rays is not particularly limited as long as the photopolymerization initiator can be activated to cause a reaction of the monomer component.

  Examples of the polymerization initiator (thermal polymerization initiator) that initiates polymerization by heating include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4-trimethylpentane, dimethyl-2,2'-azobis (2-methylpropionate, 2,2'-azobis [2-methyl-N- (phenylmethyl)- Propionamidine] dihydrochloride, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azo [2- (2-imidazolin-2-yl) propane] and other azo polymerization initiators; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dic Milperoxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 3,3,5-trimethylcyclohexa Examples thereof include peroxide polymerization initiators such as noyl peroxide and t-butyl peroxypivalate; redox polymerization initiators composed of persulfate and sodium hydrogen sulfite.

  The polymerization initiators such as the photopolymerization initiator and the thermal polymerization initiator can be used alone or in combination of two or more.

  In addition, the photocurable pressure-sensitive adhesive composition and the thermosetting pressure-sensitive adhesive composition include, in addition to the above components (a monomer component or a partial polymer thereof, a polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator). In this case, an appropriate additive may be contained. Examples of such additives include fillers, crosslinking agents (eg, known crosslinking agents such as polyisocyanate crosslinking agents, silicone crosslinking agents, epoxy crosslinking agents, alkyl etherified melamine crosslinking agents, etc.), Tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc., solid, semi-solid or liquid at room temperature), plasticizers, anti-aging agents, antioxidants, surfactants, etc. Is mentioned.

  In particular, a filler can be suitably used as an additive in order to increase the shear adhesive force or improve workability. Such a filler may be either an inorganic filler or an organic filler. The inorganic filler is not particularly limited, and examples thereof include silica, calcium carbonate, clay, titanium oxide, glass balloon, and alumina balloon. The organic filler is not particularly limited, and examples thereof include beads and balloons made of various resins such as polyester beads, polyvinylidene chloride balloons, and polyacrylic balloons.

  In addition, a crosslinking agent and a polyfunctional monomer can be used as a cross-linking agent. As such a crosslinking agent and polyfunctional monomer, those exemplified above can be used. The amount of the cross-linking agent used is 0.5% by weight or less (for example, 0.01 to 0.5% by weight, preferably the same as the amount of the polyfunctional monomer used). 0.02 to 0.3% by weight).

(Method for preparing pigment-containing resin solution)
In the pigment-containing resin liquid preparation step, the pigment-containing resin liquid is prepared by blending the pigment dispersion obtained in the pigment dispersion preparation step with the resin liquid. In preparing the pigment-containing resin liquid, the method for blending the pigment dispersion into the resin liquid is not particularly limited, and examples thereof include a method in which the pigment dispersion is added to the resin liquid with stirring and mixed. In addition, as a charging method when charging the pigment dispersion into the resin liquid, for example, a batch charging method, a split charging method (a continuous charging method, an intermittent charging method, etc.), etc. Can be mentioned.

  In the present invention, the temperature at the time of preparing the pigment-containing resin liquid is not particularly limited, and is usually room temperature, but may be higher or lower than room temperature.

[Method for producing colored sheets]
The manufacturing method of the colored sheets of this invention is a method of manufacturing colored sheets using the pigment containing resin liquid obtained through the said process (A)-(B). Colored sheets can be produced by forming a sheet using the pigment-containing resin liquid. Therefore, the manufacturing method of the colored sheets of this invention can comprise the following process (C).
Step (C): A step of producing colored sheets by forming into a sheet using a pigment-containing resin liquid (sheet forming step)

  In the step (C) (sheet formation step), the pigment-containing resin liquid obtained in the step (B) (pigment-containing resin liquid preparation step) is used to produce a sheet, thereby producing colored sheets. In the production of the colored sheets, the method for forming the sheet is not particularly limited, and is known depending on the resin component in the pigment-containing resin liquid (for example, a photocurable resin component or a thermosetting resin component). It can select suitably from the sheeting method. Specifically, for example, when the pigment-containing resin liquid is a pigment-containing resin liquid (pigment-containing photocurable resin liquid) in which a photocurable resin composition is used as the resin liquid, the pigment-containing photocurable resin liquid Is coated on a support, and then cured by irradiation with light to form a photocurable resin layer containing a pigment, whereby colored sheets (colored photocurable sheets) with a photocurable resin are formed. Can be produced. When the pigment-containing resin liquid is a pigment-containing resin liquid (pigment-containing thermosetting resin liquid) in which a thermosetting resin composition is used as the resin liquid, the pigment-containing thermosetting resin liquid is placed on the support. After coating, it is cured by heating to form a thermosetting resin layer containing a pigment, whereby colored sheets (colored thermosetting sheets) made of a thermosetting resin can be produced.

  In the present invention, when the pigment-containing resin liquid is a pigment-containing photocurable resin liquid, before forming into a sheet, a part of the monomer component in the pigment-containing photocurable resin liquid is polymerized in advance. After preparing a pigment-containing photocurable resin liquid (syrup) having a partially polymerized monomer component partially polymerized, it may be formed into a sheet.

In the production of colored photocurable sheets, the light source used for light irradiation is not particularly limited, and is a photocurable resin composition (particularly, a photopolymerization initiator) in a pigment-containing photocurable resin liquid. ) Can be appropriately selected from known light sources, such as ionizing radiation (α rays, β rays, γ rays, neutron rays, electron beams, etc.) and active energy rays such as ultraviolet rays. What can radiate | emit (especially ultraviolet rays) can be used suitably. Specifically, examples of the light source include a high pressure discharge type light source such as a metal halide lamp and a high pressure mercury lamp, and a low pressure discharge type light source such as a black light, a fluorescent lamp for trapping insects, and a chemical lamp. A light source can be used individually or in combination of 2 or more types. In such a light source, the wavelength and illuminance are not particularly limited. For example, the illuminance of light from the light source can be selected from a range of 0.1 to 500 mW / cm ² (preferably 1 to 300 mW / cm ² , more preferably 50 to 200 mW / cm ² ).

  When a pigment-containing resin liquid such as a pigment-containing photocurable resin liquid or a pigment-containing thermosetting resin liquid is applied on a support, a conventional coating machine (for example, a comma roll coater, a die roll coater, a gravure roll) is used. A coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, etc.).

  The predetermined surface of the support to which the pigment-containing resin liquid is applied can be a release surface (non-adhesive surface) of the separator or any surface of the substrate. In the present invention, when the colored sheets are composed only of a layer containing a pigment-containing resin liquid, a separator is usually used as the support on which the pigment-containing resin liquid is applied. A conventional release paper or the like can be used as the separator (release liner). Specifically, as the separator, for example, in addition to a substrate having a release treatment layer (release treatment layer) with a release treatment agent (release treatment agent) on at least one surface, a fluorine-based polymer (eg, polytetrafluoroethylene). Low adhesive substrates made of fluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer, etc. A low-adhesive substrate made of an adhesive polymer (for example, an olefin resin such as polyethylene or polypropylene) can be used. In the case of a low-adhesive substrate, both surfaces can be used as release surfaces. On the other hand, in the case of a substrate having a release treatment layer, the release treatment layer surface is changed to a release surface (release treatment surface or non-adhesive surface). Can be used as a sex processing surface).

  As the separator, for example, a separator (base material having a release treatment layer) in which a release treatment layer is formed on at least one surface of the separator base material can be suitably used. Examples of the separator substrate include polyester films (polyethylene terephthalate film, etc.), olefin resin films (polyethylene film, polypropylene film, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon film), rayon films, etc. In addition to plastic base film (synthetic resin film) and papers (quality paper, Japanese paper, kraft paper, glassine paper, synthetic paper, top coat paper, etc.), these are laminated by lamination or coextrusion. (2-3 layer composite) etc. are mentioned. As a separator substrate, a plastic substrate film (especially polyethylene terephthalate film) that can block oxygen is used when light irradiation is not performed in air or in an inert gas atmosphere. A substrate can be suitably used.

  On the other hand, the release treatment agent constituting the release treatment layer is not particularly limited, and for example, a silicone release treatment agent, a fluorine release treatment agent, a long-chain alkyl release treatment agent, or the like is used. it can. A mold release processing agent can be used individually or in combination of 2 or more types.

  In addition, as a separator, what can permeate | transmit at least the light effective in hardening the coating layer by a pigment containing resin liquid (light transmissive separator) can be used suitably. The thickness and manufacturing method of the separator are not particularly limited.

[Colored sheets]
The colored sheets obtained by the production method of the present invention are colored sheets, and have a colored resin layer (colored resin layer) with a pigment-containing resin liquid. The colored sheets may be colored sheets (colored sheets with a substrate) having a structure in which a colored resin layer is formed on at least one side (one side or both sides) of the substrate, but only the colored resin layer. Colored sheets having a structure formed from (baseless colored sheets) are preferred.

  Therefore, when the colored sheets are colored pressure-sensitive adhesive sheets, colored pressure-sensitive adhesive sheets having a configuration formed only from the colored resin layer (that is, colored base-less double-sided pressure-sensitive adhesive sheets) are suitable. Such colored substrate-less double-sided pressure-sensitive adhesive sheets have a form in which both sides of the colored pressure-sensitive adhesive layer are protected by respective separators (a form having a separator / colored pressure-sensitive adhesive layer / separator layer structure). It is preferable.

  Such colored sheets may have a form wound in a roll shape, or may have a form in which sheets are laminated. That is, the colored sheets of the present invention can have forms such as a tape shape and a sheet shape.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the following pigments, dispersants, and diluents were used. 2-ethylhexyl acrylate as a diluent is a monomer component related to a polymer obtained by polymerizing a monomer component or a part of the monomer component in a pressure-sensitive adhesive solution as a resin liquid.
(Pigment)
(1) Trade name “Microlith Black CA” (manufactured by Ciba Specialty Chemicals; containing carbon black in a proportion of 60% by weight; sometimes referred to as “Pigment A”)
(2) Trade name “Microlith Black CT” (manufactured by Ciba Specialty Chemicals; containing carbon black in a proportion of 35% by weight; sometimes referred to as “pigment B”)
(3) Product name “UTCO-595” (manufactured by Dainichi Seika Kogyo Co., Ltd .; containing carbon black in a proportion of 18% by weight; sometimes referred to as “Pigment C”)
(4) Trade name “Dymic SZ” (manufactured by Dainichi Seika Kogyo Co., Ltd .; containing carbon black in a proportion of 30% by weight; sometimes referred to as “pigment D”)
(Dispersant)
(1) Trade name “Perex TR” (manufactured by Kao Corporation; containing alkyl sulfosuccinate; sometimes referred to as “dispersant A”)
(2) Trade name “Plysurf 208F” (Daiichi Kogyo Seiyaku Co., Ltd .; containing polyoxyethylene alkyl ether phosphate; sometimes referred to as “dispersant B”)
(3) Trade name “Sorgen 30” (Daiichi Kogyo Seiyaku Co., Ltd .; containing sorbitan fatty acid ester; sometimes referred to as “dispersant C”)
(4) Trade name “Emulgen 104P” (manufactured by Kao Corporation; containing polyoxyethylene alkyl ether; sometimes referred to as “dispersant D”)
(5) Trade name “Neugen EA140” (Daiichi Kogyo Seiyaku Co., Ltd .; containing polyoxyethylene alkylphenyl ether; sometimes referred to as “dispersant E”)
(Diluent)
(1) 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd .; may be referred to as “Diluent A”)

Example 1
Diluent A as a diluent: 95 parts by weight, 5 parts by weight of Pigment A as a pigment, and 1 part by weight of Dispersant A as a dispersant are mixed and stirred for 5 minutes with a propeller mixer. A dispersion was obtained.

  In addition, as a monomer component, a product name “Irgacure 651” (manufactured by Ciba Specialty Chemicals) is used as a photopolymerization initiator in a monomer mixture in which 90 parts by weight of 2-ethylhexyl acrylate and 10 parts by weight of acrylic acid are mixed. : After 0.2 part by weight was mixed and mixed, ultraviolet rays (UV) were irradiated in a nitrogen atmosphere to prepare a partially (partially) polymerized composition (syrup). The polymerization rate of this syrup was determined to be 8%.

  The syrup: 100 parts by weight, as a photopolymerization initiator, trade name “Irgacure 184” (manufactured by Ciba Specialty Chemicals): 0.2 parts by weight, 1,6-hexanediol diacrylate (multiple as a cross-linking agent) Functional monomer): 0.15 parts by weight and the pigment dispersion: 0.2 parts by weight were mixed to prepare a colored adhesive solution (photo-curable adhesive composition).

  And after defoaming the colored adhesive solution, it is dried and applied to the non-adhesive treated surface of the polyethylene terephthalate film (thickness: 50 μm) subjected to non-adhesive treatment as a separator with a roll coater. Coating is performed so that the thickness after curing is 0.8 mm to form an uncured photocurable colored adhesive layer, and a non-adhesive as a separator is formed on the photocurable colored adhesive layer. A film made of polyethylene terephthalate (thickness: 50 μm) that has been subjected to a property treatment is laminated in such a manner that the non-tacky treated surface is in contact with the surface of the photo-curing colored pressure-sensitive adhesive layer, and an uncured photo-curing colored pressure-sensitive adhesive layer A member for a photo-curing colored pressure-sensitive adhesive sheet (uncured photo-curing colored pressure-sensitive adhesive sheet; sometimes referred to as “web”) was prepared.

The web was irradiated with ultraviolet rays by a metal halide lamp (light source) having a maximum illuminance of about 100 mW / cm ² to be completely cured to obtain a colored photo-curable double-sided pressure-sensitive adhesive sheet of a baseless type.

(Example 2)
Diluent A as a diluent: 95 parts by weight, 5 parts by weight of Pigment A as a pigment, and 1 part by weight of Dispersant B as a dispersant are mixed and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Example 3)
Diluent A as a diluent: 90 parts by weight, Pigment C as a pigment: 10 parts by weight and Dispersant A as a dispersant: 1 part by weight are mixed with a propeller mixer and stirred for 5 minutes. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

Example 4
Diluent A as a diluent: 85 parts by weight, Pigment C as a pigment: 15 parts by weight and Dispersant B as a dispersant: 1 part by weight are mixed with a propeller mixer and stirred for 5 minutes. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Example 5)
Diluent A as a diluent: 90 parts by weight, Pigment D as a pigment: 10 parts by weight and Dispersant A as a dispersant: 1 part by weight are mixed with a propeller mixer and stirred for 5 minutes. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Example 6)
Diluent A as a diluent: 90 parts by weight, Pigment D as a pigment: 10 parts by weight, Dispersant C as a dispersant: 1 part by weight, and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Example 7)
Diluent A as a diluent: 90 parts by weight, Pigment B as a pigment: 10 parts by weight, Dispersant A as a dispersant: 1 part by weight, and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Comparative Example 1)
A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that 0.01 parts by weight of pigment A as a pigment was used instead of the pigment dispersion. A baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that was used. That is, in Comparative Example 1, a commercially available pigment was used as it was without preparing a pigment dispersion using a specific dispersant or diluent. More specifically, only a pigment is mixed in a syrup with a photopolymerization initiator or a cross-linking agent without a dispersant or a diluent to prepare a colored adhesive solution, and the colored adhesive Using the agent solution, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was prepared.

(Comparative Example 2)
A colored adhesive solution was prepared in the same manner as in Example 1 except that 0.02 part by weight of pigment B as a pigment was used instead of the pigment dispersion, and the colored adhesive solution was used. A baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that was used. That is, in Comparative Example 2, as in Comparative Example 1, a pigment dispersion was not prepared using a specific dispersant or diluent, and a commercially available pigment was used as it was.

(Comparative Example 3)
A colored adhesive solution was prepared in the same manner as in Example 1 except that 0.03 part by weight of pigment C as a pigment was used instead of the pigment dispersion, and the colored adhesive solution was used. A baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that was used. That is, in Comparative Example 3, as in Comparative Example 1, a commercially available pigment was used as it was without preparing a pigment dispersion using a specific dispersant or diluent.

(Comparative Example 4)
A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that 0.02 part by weight of pigment D as a pigment was used instead of the pigment dispersion, and the colored pressure-sensitive adhesive solution A baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that was used. That is, in Comparative Example 4, as in Comparative Example 1, a pigment dispersion was not prepared using a specific dispersant or diluent, and a commercially available pigment was used as it was.

(Comparative Example 5)
Diluent A as a diluent: 95 parts by weight and 5 parts by weight of Pigment A as a pigment were blended and stirred for 5 minutes with a propeller mixer to obtain a pigment dispersion. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced. That is, in Comparative Example 5, a pigment dispersion prepared by blending a commercially available pigment in a diluent is used without preparing a pigment dispersion using a specific dispersant.

(Comparative Example 6)
Diluent A as a diluent: 90 parts by weight and 10 parts by weight of a pigment B as a pigment were blended and stirred for 5 minutes with a propeller mixer to obtain a pigment dispersion. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced. That is, in Comparative Example 6, a pigment dispersion prepared by blending a commercially available pigment in a diluent is used without preparing a pigment dispersion using a specific dispersant.

(Comparative Example 7)
Diluent A as a diluent: 85 parts by weight and 15 parts by weight of Pigment C as a pigment were blended and stirred for 5 minutes with a propeller mixer to obtain a pigment dispersion. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced. That is, in Comparative Example 7, a pigment dispersion prepared by blending a commercially available pigment in a diluent is used without preparing a pigment dispersion using a specific dispersant.

(Comparative Example 8)
Diluent A as a diluent: 90 parts by weight of pigment D: 10 parts by weight of pigment D as a pigment were mixed and stirred with a propeller mixer for 5 minutes to obtain a pigment dispersion. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced. That is, in Comparative Example 8, a pigment dispersion prepared by blending a commercially available pigment in a diluent is used without preparing a pigment dispersion using a specific dispersant.

(Comparative Example 9)
Diluent A as a diluent: 95 parts by weight, 5 parts by weight of Pigment A as a pigment, and 1 part by weight of Dispersant D as a dispersant are mixed and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Comparative Example 10)
Diluent A as a diluent: 95 parts by weight, 5 parts by weight of Pigment A as a pigment, and 1 part by weight of Dispersant E as a dispersant are mixed and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Comparative Example 11)
Diluent A as a diluent: 85 parts by weight, Pigment C as a pigment: 15 parts by weight, Dispersant D as a dispersant: 1 part by weight, and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Comparative Example 12)
Diluent A as a diluent: 85 parts by weight, Pigment C as a pigment: 15 parts by weight, Dispersant E as a dispersant: 1 part by weight, and stirred for 5 minutes with a propeller mixer. A dispersion was obtained. A colored pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that this pigment dispersion was used, and the same as in Example 1 except that the colored pressure-sensitive adhesive solution was used. Thus, a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet was produced.

(Evaluation)
About the base-less type colored photo-curing type double-sided pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, after removing the separator, using a digital microscope (manufactured by Keyence Corporation) at a magnification of 100 times, any Were observed, the presence or absence of a black granular portion was confirmed, and the case where there was no black granular portion was evaluated as “◯”, and the case where there was a black granular portion was evaluated as “x”. Of course, when there is no black granular part, the dispersibility of the pigment (carbon black) is good, and when there is a black granular part, the dispersibility of the pigment is poor. The evaluation results are shown in Table 1.

  As a good example of dispersibility, a photograph of a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet according to Example 1 observed using a digital microscope (magnification: 100 times) is shown in FIG. It was shown to. In addition, as a poor dispersibility example, a photograph of a baseless-less colored photocurable double-sided pressure-sensitive adhesive sheet according to Comparative Example 1 observed using a digital microscope (magnification: 100 times) is shown in FIG. Indicated. Although the black granular portion does not exist in FIG. 1, it is confirmed in FIG. 2 that the black granular portion exists in a portion surrounded by a dotted line.

  As is clear from Table 1, the pigment-free photo-curing type double-sided pressure-sensitive adhesive sheet according to the example was observed with a microscope (magnification: 100 times), and as a result, no carbon black particles were observed. It was confirmed that the dispersibility of the pigment was very good. Therefore, the pigment can be blended in the resin liquid with excellent dispersibility by blending the pigment into the resin liquid using the pigment dispersion liquid of the pigment, the specific dispersant, and the diluent. It was confirmed that colored sheets colored with excellent colorability can be produced.

It is a figure which shows the photograph regarding the base material-less type colored photocurable double-sided adhesive sheet which concerns on Example 1. FIG. It is a figure which shows the photograph regarding the base material-less type colored photocurable double-sided adhesive sheet which concerns on the comparative example 1. FIG.

Claims (11)

A method for producing colored sheets using a resin liquid containing a pigment, comprising the following steps (A) to (B).
Step (A): A pigment dispersion is prepared by mixing a pigment, at least one dispersant selected from alkyl sulfosuccinate, polyoxyethylene alkyl ether phosphate ester salt and sorbitan fatty acid ester, and a diluent. Step (B): Step of preparing the resin liquid containing the pigment by blending the pigment dispersion into the resin liquid The method for producing colored sheets according to claim 1, wherein the resin liquid is a solvent-free resin liquid substantially not containing an organic solvent. The method for producing colored sheets according to claim 1 or 2, wherein the liquid component of the resin liquid is a liquid component containing at least a monomer component of a photocurable resin or a thermosetting resin or a partial polymer thereof. The method for producing colored sheets according to claim 3, wherein the monomer component of the photocurable resin or the thermosetting resin is an acrylic monomer component. The method for producing colored sheets according to any one of claims 1 to 4, wherein the pigment contains at least carbon black. The method for producing colored sheets according to any one of claims 1 to 5, wherein a pigment composition in which a pigment is dispersed in a resin component is used as the pigment. The method for producing colored sheets according to any one of claims 1 to 6, wherein the diluent contains at least the same liquid component as the main component of the liquid component in the resin liquid. The ratio of a dispersing agent is 1 to 50 weight% with respect to the pigment whole quantity, The manufacturing method of the colored sheets in any one of Claims 1-7. The method for producing colored sheets according to any one of claims 1 to 8, wherein a ratio of the diluent is a ratio of pigment: diluent (weight ratio) = 1: 99 to 80:20. The method for producing colored sheets according to any one of claims 1 to 9, wherein the colored sheets are colored pressure-sensitive adhesive sheets. The method for producing a colored sheet according to any one of claims 1 to 10, wherein the colored pressure-sensitive adhesive sheets are colored pressure-sensitive adhesive sheets having a configuration formed only from a colored pressure-sensitive adhesive layer.

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