JPH08283653A - Surface-treating agent - Google Patents

Abstract

PURPOSE: To obtain a surface-treating agent, printing agent or cloth-printing agent containing the copolymer of two kinds of monomers having specific structures and used for treating various kinds of substrates to impart good water absorption, printing characteristics, cloth-printing characteristics, etc., thereto. CONSTITUTION: The surface-treating agent contains a copolymer comprising (A) a monomer of formula I (R<1> is H, methyl; R<2> is H, a lower alkyl) [preferably 2-hydroxyethyl (meth)acrylate] and (B) a radically polymerizable monomer having at least two oxyalkylene groups in the molecule, preferably a monomer of formula II (R<3> is H, methyl; R<4> is hydroxy, an alkoxy, phenoxy, etc.; n is an integer of >=2), or preferably a monomer of formula III (R<5> is a 1-6C alkylene; A is a structural unit between the NCO groups of a diisocyanate compound; m is an integer of >=2). The components A and B preferably contained in a total amount of >=50wt.% inn the copolymer composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treating agent, a printing material and a printing material, and more specifically, by treating various base materials, the surface characteristics of the base material, such as water absorption, printing characteristics, and printing. The present invention relates to a surface-treating agent capable of improving properties and the like, and a printing material and a printing material which can be printed with an aqueous ink or printed with an aqueous dye and do not deteriorate in printing or printing characteristics under the influence of humidity. .

[0002]

2. Description of the Related Art Synthetic polymers such as polyester, acrylic and nylon are generally hydrophobic, and the affinity and penetrability of aqueous dyes and aqueous inks for them are extremely low. Therefore, for example, even if a polyester film is printed by an ink jet printer or the like, the water-based ink does not fix on the surface of the film, and thus it is difficult to print with high resolution.

As a method for improving the affinity of such a hydrophobic substrate for aqueous ink, fine particles of SiO ₂ or CaO are added to a hydrophilic binder such as polyvinyl alcohol, polyvinylpyrrolidone, carboxystarch or carboxymethylcellulose. A method of applying the dispersed substance to the surface of a hydrophobic substrate and a method of treating the surface of the hydrophobic substrate with a silane coupling agent are known.
According to these methods, the printability with respect to the water-based ink can be improved to some extent.

However, the improvement effect by these methods is not yet sufficient. Further, in the modification with the silane coupling agent, since the silane coupling compound is extremely expensive, it is costly to modify the hydrophobic substrate, and the printing material such as the printing film to be produced is inevitably used. There was a problem of becoming expensive. Furthermore, since the surface of the obtained printing material is extremely sensitive to moisture,
When the surface of the film was touched with bare hands, there were problems in handling such as fingerprint marks being attached due to the humidity of the hand, and the printing characteristics could not be maintained for a long time. Furthermore, since the transparency of the transparent substrate is impaired by the treatment with the silane coupling agent, it is impossible to produce an OHP film having excellent transparency even though printing with an aqueous ink is possible. There was also.

Further, there is a similar problem in the printing of synthetic polymer fiber cloths, sheets and the like. That is, it is difficult to print a synthetic polymer fiber cloth with an aqueous dye, and there is a problem that a complicated pattern cannot be printed with high resolution and high resolution.

[0006] In printing, conventionally known is a method of improving the permeability of the printing paste into the synthetic fiber cloth by treating the synthetic fiber cloth in advance with a penetrant containing a low-molecular nonion or anion. . However, the penetrant easily drops off from the cloth surface, and the dye oozes out, resulting in a problem that the sharpness of the pattern and the resolution are significantly lowered. In addition, JP-A-54-
Japanese Patent No. 93176 discloses that printing is performed by using a printing paste containing a specific printing aid. However, even in this case, there was a problem similar to the method using the penetrant.

The present invention has been completed under these circumstances. That is, an object of the present invention is to solve the above-mentioned conventional problems. An object of the present invention is to provide a surface treating agent which can improve surface properties of a hydrophobic substrate, such as water absorption, printing properties and printing properties, by treating various substrates. The object of the present invention is to improve the affinity and penetrability to these water-based inks by treating a printing base made of a synthetic polymer, and to provide suitable properties capable of supporting high-speed printing. It is to provide a surface treatment agent for a substrate.
Further, the present invention has excellent penetrability into a printing substrate,
It is an object of the present invention to provide a surface treating agent for a printing substrate, which can improve the printing property, level dyeing property, sharpness, etc. of the printing substrate with an aqueous dye.

Further, an object of the present invention is to provide a printing material capable of high-speed printing with high resolution using an aqueous ink by an ink jet printer or the like, and also having affinity with an aqueous dye, printing ability, and evenness. An object of the present invention is to provide a printing material which is excellent in dyeability and sharpness and can be suitably used for printing a pattern having a complicated pattern.

[0009]

The invention according to claim 1 for solving the above-mentioned problems is defined by the following general formula (1):

[0010]

Embedded image

(Wherein R ¹ represents a hydrogen atom or a methyl group and R ² represents a hydrogen atom or a lower alkyl group) and a radical having at least two oxyalkylene groups in the molecule. A surface treatment agent comprising a copolymer having a polymerizable monomer. The invention according to claim 2, wherein the monomer represented by the chemical formula 1 and at least two in the molecule are included. The radical-polymerizable monomer having an oxyalkylene group is the surface treatment agent according to claim 1, which is contained in the copolymerization composition in an amount of 50% by weight or more. The radical-polymerizable monomer having at least two oxyalkylene groups in is a monomer having at least two oxyalkylene groups and a polymerizable double bond in the molecule. The surface treating agent according to claim 1 or 2, wherein the radical-polymerizable monomer having at least 2 mol of an oxyalkylene group in the molecule has the following general formula: (2)

[0012]

Embedded image

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydroxyl group, an alkoxy group, a phenoxy group,
Indicates a carboxyl group. n is an integer of 2 or more. The surface treating agent according to claim 1 or 2, which is a monomer represented by the formula (1). The invention according to claim 5 is characterized in that the radically polymerizable monomer having at least 2 mol of an oxyalkylene group in the molecule is , The following general formula (3)

[0014]

Embedded image

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydroxyl group, an alkoxy group, a phenoxy group,
It shows a carboxyl group and R ⁵ shows an alkylene group having 1 to 6 carbon atoms. A is N in the diisocyanate compound
The structure between CO groups is shown. m is an integer of 2 or more. )
The surface treating agent according to claim 1 or 2, which is any one of the monomers represented by the following. The invention according to claim 6 is a radical-polymerizable compound having at least 2 mol of an oxyalkylene group in the molecule. The monomer is a monomer obtained by reacting an NCO-terminated urethane prepolymer obtained by reacting a polyoxyethylene glycol with a diisocyanate compound with the acrylate or methacrylate represented by the general formula (1). The surface treatment agent according to claim 1 or 2, wherein the invention according to claim 7 is the surface treatment agent according to claim 1.
A printing material, which is treated with the surface treatment agent according to any one of claims 1 to 6, and the invention according to claim 8 is treated with the surface treatment agent according to any one of claims 1 to 6. It is a printing material.

These inventions will be described in detail below.

(1) Surface Treatment Agent As the monomer represented by the general formula (1), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate etc. can be mentioned. Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable. In the general formula (1), the lower alkyl group as R ² is preferably a lower alkyl group having 1 to 5 carbon atoms, among which a methyl group, an ethyl group, a propyl group, an isopropyl group and the like are preferable. Most preferably, R ^{2 in the} general formula (1) is a hydrogen atom.

The radical-polymerizable monomer having at least two oxyalkylene groups in the molecule is, for example, a monoacrylate having two or more oxyalkylene groups in the molecule, for example, an oxyethylene group or an oxypropylene group. Monomethacrylate can be preferably adopted. Among these, monoacrylate having at least two oxyethylene groups in the molecule is preferable.

The oxyalkylene group may be present in these molecules in such a manner that two or more oxyalkylene groups are present continuously, or in a state where they are separated by another structure. It may be an existing mode. Further, it may have two or more of either oxyethylene group or oxypropylene group in the molecule, or it may have both of oxyethylene group and oxypropylene group and the total number of moles is 2 or more. It may be.

The number of oxyalkylene groups in this monomer molecule is not particularly limited as long as it is 2 or more, but usually 2 to
The number is 50, preferably 3 to 30, and particularly preferably 3 to 20. When the number of oxyalkylene groups is within this range, excellent penetrability and affinity can be imparted to the surface of the synthetic polymer substrate having a low surface energy property, and the printability by the aqueous ink or the aqueous dye can be improved. Or especially excellent in printability.

Examples of the monomer having at least two oxyethylene groups in the molecule include a monoacrylate or monomethacrylate represented by the general formula (2), a monoacrylate or a monoacrylate represented by the general formula (3). Methacrylate etc. can be mentioned.

Further, as the monomer having at least two oxyethylene groups in the molecule, the following general formula (4)

[0023]

[Chemical 4]

(However, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydroxyl group, an alkoxy group, a phenoxy group,
Indicates a carboxyl group. A represents a structure between NCO groups in a diisocyanate compound described later. n is an integer of 2 or more. The monomer represented by () can also be suitably adopted.

Of the groups represented by R ⁴ in the above general formulas (2) to (4), the alkoxy group is a methoxy group,
A lower alkoxy group such as an ethoxy group is preferable, and a methoxy group is particularly preferable. In the general formulas (2) to (4), R ⁴
Among the groups represented by, the phenoxy group may be a phenoxy group having no substituent or a phenoxy group having a substituent such as a hydroxyl group or a lower alkyl group.

N in the general formula (3) or (4) is
It is usually 2 to 30, preferably 3 to 25, and particularly preferably 3 to 20. When n is within such a range, the hydrophobic substrate can be provided with particularly excellent water absorption and permeability.

The monomer represented by the general formula (2) is
For example, acrylic acid or methacrylic acid and the general formula H-
_{(O-CH 2 CH 2)} n -R 4 ( provided that, R ⁴ and n
Represents the same meaning as described above. ) It can be obtained by reacting with a polyoxyethylene compound. Examples of the monomer represented by the general formula (3) include acrylic acid or methacrylic acid and the general formula H- (O-CH
₂ CH _{2) n} -R ⁴ (where urethane R ⁴ and n have a NCO-terminated obtained by reacting a diisocyanate compound described later polyoxyethylene compound represented by represents.) The same as defined above Polymer,
For example, it can be obtained by reacting with the acrylate or methacrylate represented by the general formula (1).

The monomer represented by the general formula (4) is
For example, acrylic acid or methacrylic acid and the general formula H-
_{(O-CH 2 CH 2)} n -R 4 ( provided that, R ⁴ and n
Represents the same meaning as described above. The polyoxyethylene compound represented by (4) and the diisocyanate compound described below are reacted to react with an isocyanate compound which is a urethane prepolymer having an NCO terminal and acrylic acid or methacrylic acid.

Examples of the diisocyanate compound include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HD
I), dodecamethylene diisocyanate, 2,2,4-
Trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis (2-isocyanate ethyl) fumarate, bis (2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, etc. Aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding carbons in NCO groups; the same applies hereinafter); for example, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, etc., having 4 carbon atoms. Alicyclic polyisocyanate having 15 to 15 carbon atoms such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, diethylbenzene diisocyanate, etc.
12 araliphatic polyisocyanates; trimers of IPDI and HDI; for example, tolylene diisocyanate (TDI), crude TDI, diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, and other aromatic polyisocyanates having 6 to 20 carbon atoms. Can be mentioned.

The reaction of said polyoxyethylene compound, eg polyoxyethylene glycol, with a diisocyanate compound is carried out to produce a urethane prepolymer,
As such, the reaction can be carried out under conventionally known reaction conditions.

In the present invention, at least 2 in the molecule
As the radically polymerizable monomer having one oxyalkylene group, a monomer represented by the following general formula (5) can also be preferably used.

[0032]

Embedded image

(In the above formula, R ⁶ and R ⁷ are each a lower alkyl group, and they may be the same or different, and p represents an integer of 10 or less.) Examples of the monomer represented by the formula (5) include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and polyethylene glycol dimethacrylate.

In the present invention, as the radically polymerizable monomer having at least two oxyalkylene groups in the molecule, the monomer represented by the general formula (2) and the monomer represented by the general formula (3) are used. , And the monomer represented by the general formula (4) can be mentioned as preferred examples.

The monomers mentioned as these preferable examples can adjust the affinity of the monomer for water, the film strength, and the affinity for the substrate by combining with a urethane compound whose chemical structure can be designed relatively freely. Since it has the advantage that it can be used, it is advantageous as a surface treatment agent.

The copolymer contained in the surface treating agent of the present invention includes a monomer represented by the general formula (1) (hereinafter sometimes referred to as "monomer (A)") and at least two in the molecule. The oxyalkylene group-containing radically polymerizable monomer (hereinafter sometimes referred to as “monomer (B)”) can be obtained by adding another monomer to cause a reaction.

When another monomer is blended as a copolymerization component, the affinity for the surface of the substrate, the flexibility of the film, and the film are higher than those of the copolymer composed of only the monomer (A) and the monomer (B). The strength and water absorption may be further improved.

The ratio of the monomer (A) and the monomer (B) in this case is not particularly limited, but the content of the monomer (A) is 20 relative to the total amount of the monomer (A) and the monomer (B). ~ 90 wt%, preferably 35
75% by weight, and the content of the monomer (B) is 80 to 1
It is 0% by weight, preferably 65 to 25% by weight.

When the ratio of the monomer (A) to the monomer (B) is within the above range, the surface modification effect of the hydrophobic base material is excellent, and for example, the surface of the hydrophobic base material is sufficient for the aqueous dye and the aqueous ink. It is possible to impart high permeability and affinity.
Therefore, the surface characteristics of the printing material obtained by treating the printing substrate with this surface treatment agent become suitable for printing using an aqueous ink in particular, and the printing substrate is treated with this surface treatment agent. The surface properties of the obtained printing material become suitable for printing using an aqueous dye.

The copolymer in the present invention may contain other monomer (C) in addition to the monomer (A) and the monomer (B) as long as the object of the present invention is not impaired.

Examples of the other monomer (C) include acrylic acid, methacrylic acid, acrylamide, vinylpyrrolidone, vinylpyridine, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate. You can

When another monomer (C) is contained as a copolymerization component in the copolymer, the content ratio of the copolymerization component is such that the monomer (A) and the monomer (B) are contained.
Is 50% by weight or more, preferably 60% by weight or more, and the content of the other monomer (C) is less than 50% by weight, preferably less than 40% by weight.

The surface treating agent of the present invention may contain the copolymer having the monomer (A) and the monomer (B) in any proportion as long as the object of the present invention can be achieved. Although good, the content ratio of the copolymer is at least 50% by weight, preferably 50 to 95%.
%, More preferably 50 to 90% by weight. When the content ratio of the copolymer is within this range,
Particularly, it is excellent in the effect of modifying the surface characteristics of the hydrophobic substrate.

In the present invention, the copolymer may be contained in the surface treatment agent at a ratio of 100% by weight.
In this case, the surface treatment agent is the copolymer itself containing the monomer (A) and the monomer (B). The surface treatment agent containing 100% by weight of this copolymer is a solid or paste material containing no solvent or other additives. Therefore, the surface treatment agent containing 100% by weight of this urethane resin has good storability. The solid or pasty surface treatment agent may be diluted with an appropriate solvent to an appropriate concentration before use.

The surface treating agent of the present invention contains, in addition to the copolymer having the monomer (A) and the monomer (B), other additives and the like within a range not impairing the object of the present invention. Is also good.

Examples of the additives include hydrolysis inhibitors, antioxidants, ultraviolet absorbers, antifungal agents, and inorganic compound powders. As a hydrolysis inhibitor for preventing hydrolysis, for example, carbodiimide type stavaxol 1, PCD (manufactured by Bayer), 4-t-
Examples thereof include butyl catechol, azodicarbonamid, azodicarboxylic acid ester, and fatty acid amide. Examples of antioxidants for preventing deterioration due to oxidation include BHT, Irganox 1010, Irgano.
x1076, Cyanox 1790, Irganox 259, DLTDP, D
STDP, Santonox R, Irganox 1035, TPP and the like can be mentioned. Examples of UV absorbers for preventing deterioration due to UV irradiation include Viosorb 100 and Vi.
osorb 130, Viosorb 120, Cyasorb UV-24, Tinuvin
P, Tinuvin 320, Tinuvin 327, Viosorb 510, Uvinu
l 400, Uvinul D-50, Bayer 317 and the like. Examples of the mildew-proofing agent for preventing the growth of mold include pentachlorophenol, pentachlorophenol laurate, copper-8-hydroxyquinoline, bis (tri-
n-Butyltin) and the like. Examples of the inorganic compound include silica, alumina, calcium carbonate,
Examples thereof include talc and magnesium oxide.

When the above-mentioned additive is blended, its content is usually 0.05 to 5% by weight, preferably 0.2 to 3
% By weight.

The surface treating agent preferably contains a solvent in order to improve workability. By containing the solvent, brush coating, spray coating, padding treatment, coating with a bar coater, dipping treatment and the like can be performed with good workability. Water and / or an organic solvent can be used as the solvent.

Examples of water used as a solvent include distilled water, ion-exchanged water, and ammonia water.

As the organic solvent, for example, methanol,
Various alcohols including lower alcohols such as ethanol and propanol, various ketones such as lower alkyl ketones such as acetone, ketone and methylpropyl ketone, monocyclic aromatic hydrocarbons such as benzene, toluene and xylene And other amide solvents such as aromatic hydrocarbons, dimethylformamide and formamide, and n
Examples thereof include aliphatic solvents such as hexane and heptane.

Among these, distilled water, ion-exchanged water,
Water such as ammonia water, various alcohols including lower alcohols such as methanol, ethanol and propanol, various ketones such as acetone, ketones and lower alkyl ketones such as methylpropyl ketone, benzene, toluene, xylene Monocyclic aromatic hydrocarbons such as, and ion-exchanged water, ammonia water, methanol, ethanol, propanol, benzene, toluene,
And at least one selected from the group consisting of xylene.

Water and an organic solvent miscible with water are referred to as an aqueous solvent. The surface treating agent which is a mixture of the copolymer having the monomer (A) and the monomer (B) and the aqueous solvent is It is safe with no risk of fire during manufacture, storage and use.

The surface treatment agent which is a mixture of a copolymer containing the monomer (A) and the monomer (B) and a solvent is
Although it cannot be unconditionally determined depending on the contents of the monomer (A) and the monomer (B), the type of solvent, and the like, it is in an emulsion state or a solution state.

The surface-treating agent in the emulsion state and the water-soluble surface-treating agent which can be made into an aqueous solution are hydrophobic substrates such as a printing substrate and a printing substrate without using an organic solvent. Since it can be applied to the elastic material, the working environment can be made suitable and the handling becomes easy. The solution-state surface treatment agent has an advantage that a uniform coating film can be easily formed when applied to a synthetic polymer material having a low surface energy.

—Surface Treatment with Surface Treatment Agent— As a method for treating a substrate with the surface treatment agent of the present invention, a film or thin film derived from the surface treatment agent of the present invention is formed on at least the surface of the substrate. There is no particular limitation as long as it can.

For example, when the surface treatment agent has sufficient fluidity, it is applied to the surface of the substrate as it is, and when it does not have fluidity, it is diluted with various solvents to adjust the viscosity, and By coating the surface of the material, surface treatment of various base materials can be performed.

The coating method in this case is not particularly limited, and conventionally known methods such as brush coating, spray coating, padding treatment, coating with a bar coater and dipping can be employed.

Drying after coating may be carried out by natural drying, a method of drying by blowing hot air or cold air, a method of drying under reduced pressure, or the like.

Examples of the substrate treated with the surface treating agent of the present invention include hydrophobic substrates made of synthetic polymers such as polyester, acryl and nylon. Also,
The shape of the hydrophobic substrate is not particularly limited, and may be a fiber cloth, a film or a sheet.

—Printing Material— The printing material of the present invention can be produced by subjecting a printing substrate to a surface treatment with the above surface treating agent.

As the printing substrate, a film or sheet made of a synthetic polymer such as a polyolefin resin such as polyethylene or polypropylene, a polyester, an acetate resin, an acrylic resin or a polycarbonate resin, or a fiber derived from ordinary natural pulp is mainly used. As the component, neutral or acidic high-quality paper, medium-quality paper, recycled paper coated paper, art paper, or a film or sheet-like material known per se in the art can be adopted without particular limitation.

The treatment with the surface treatment material is as described above.
It can be carried out by coating or the like without particular limitation.

The printing material of the present invention has an improved affinity for the water-based ink on its surface and can be suitably used for printing using a water-based ink or a water-soluble paint. In particular, it can be suitably used for printing with an inkjet printer, and clear printing with high resolution is possible. It is also suitable for high speed printing.

Further, the fixability of the water-based ink is good, and the color fading due to touch with hands and the fading due to long-term storage are extremely small.

—Printing Material— The printing material of the present invention can be produced by subjecting a printing substrate to a surface treatment with the above-mentioned surface treatment agent.

As the printing substrate, a fiber cloth, film or sheet made of synthetic polymer such as polyolefin resin such as polyethylene or polypropylene, polyester, acetate resin, acrylic resin or polycarbonate resin can be adopted.

The treatment with the surface treatment material is the same as in the printing material.

The printing material of the present invention has an improved affinity for the water-based ink on its surface and can be suitably used for printing using a water-based dye or the like. That is, clear printing with high resolution is possible. In addition, the fixability of the dye is good, and the color fading due to touch with hands and the fading due to long-term storage are extremely small.

[0069]

【Example】

(1) Printing test (Example 1) 2-hydroxyethyl methacrylate 80
Parts by weight and the following formula (6)

[0070]

[Chemical 6]

20 parts by weight of the compound represented by the formula (2) was dissolved in 200 parts by weight of isopropyl alcohol, and 2,2'-
By adding 3 parts by weight of azobisisobutyronitrile (AIBN) and reacting at 65 ° C. for 4 hours, a reaction liquid containing a copolymer was obtained. The reaction solution was directly used as a surface treatment agent.

The surface treating agent thus obtained was applied to a 70 μm thick polyester film with a 50 μ applicator and dried at 100 ° C. for 2 minutes to obtain a printing film.

-Appearance and Fingerprint Adhesion- The appearance and fingerprint adhesion of this printing film were evaluated as follows, and the evaluation results are shown in Table 1.

<Appearance of Printing Film> The printing film before printing was visually observed to determine its transparency.

<Fingerprint Adhesion> After the thumb's belly was pressed against the surface treatment agent coated surface of the printing film before printing for 20 seconds, the state of fingerprint adhesion was visually observed and evaluated according to the following criteria.

◯: No fingerprint remains at all Δ: Thin fingerprint trace remains ×: Fingerprint trace remains clearly

-Resolution, Dryness and Scratch Resistance- The obtained printing film was color printed with a color jet printer (Epson's MACHJET COLOR, model number MJ-700V2C). The resolution, drying property and scratch resistance of the printing film after printing were evaluated as follows, and the evaluation results are shown in Table 1.

<Resolution> The state of the printing film after printing was visually observed and the resolution was evaluated according to the following criteria.

◯: The printed pattern has no bleeding and the boundary line between the patterns is clear.

Δ: The printed pattern has bleeding and the boundary line between the patterns is unclear.

X: There is a repelling of the print pattern.

<Drying property> After 30 seconds from the completion of printing and 3 minutes after the completion of printing, the printing surface of the printing film was wiped with a cloth to check whether the ink was discolored, and the drying property was determined according to the following criteria. Was evaluated.

◯: No color fading after 30 seconds and extremely excellent in drying property Δ: Color fading after 30 seconds but no color fading after 3 minutes x: Color fading remarkable after 3 minutes

<Scratch resistance> After printing, after allowing to stand for 5 minutes to dry, the printed surface was scratched with a nail, and the ease of peeling of the ink or surface treatment agent at this time was examined to evaluate the scratch resistance. did. The scratch resistance was evaluated according to the following criteria.

◯: Almost no peeling occurs even when strongly scratched, and extremely excellent in scratch resistance Δ: Not easily peeled, but peeling occurs due to strong scratching ×: Easy peeling, extremely poor scratch resistance .

Example 2 A printing film was prepared in the same manner as in Example 1 except that the following reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

2-hydroxyethyl methacrylate 90
Weight part and the following formula (7)

[0088]

[Chemical 7]

A pre-emulsion solution containing 10 parts by weight of the compound represented by the formula, 3 parts by weight of sodium dodecylbenzene sulfonate, 2 parts by weight of a 7 mol adduct of nonylphenol with ethylene oxide, and 150 parts by weight of deionized water was previously prepared. Prepared.

To 50 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium peroxide and 0.05 parts by weight of potassium acid sulfite were added, the temperature was raised to 65 ° C. with stirring, and the pre-emulsion solution was added dropwise thereto. While carrying out the polymerization reaction. A reaction solution obtained by continuing the polymerization reaction for an additional 180 minutes after the completion of dropping.

Example 3 A printing film was prepared in the same manner as in Example 1 except that the following reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

95 parts by weight of 2-hydroxyethyl acrylate and the following formula (8)

[0093]

Embedded image

5 parts by weight of the compound represented by the above are dissolved in 200 parts by weight of methanol, 3 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) is added, and the mixture is reacted at 65 ° C. for 4 hours. The reaction solution obtained.

Example 4 A printing film was prepared in the same manner as in Example 1 except that the following reaction solution was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

90 parts by weight of 2-hydroxyethyl acrylate, a urethane prepolymer obtained by reacting an ethylene oxide propylene oxide adduct of butanol with hexamethylene diisocyanate according to a conventional method and 2
10 parts by weight of a compound obtained by reacting with -hydroxyethyl acrylate was dissolved in 200 parts by weight of methanol, and 2,2'-azobisisobutyronitrile (AIB
N) A reaction liquid obtained by adding 3 parts by weight and reacting at 65 ° C. for 4 hours.

Example 5 A printing film was prepared in the same manner as in Example 1 except that the following reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

2-hydroxyethyl methacrylate 85
Parts by weight, 5 parts by weight of methyl methacrylate, 5 parts by weight of the compound represented by the general formula (7), and the formula (8)
5 parts by weight of the compound represented by the formula (1) were dissolved in 200 parts by weight of methanol, 3 parts by weight of 2,2′-azobisisobutyronitrile (AIBN) was added, and the mixture was reacted at 65 ° C. for 4 hours. Reaction liquid.

Example 6 A printing film was prepared in the same manner as in Example 1 except that the following reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

85 parts by weight of 2-hydroxyethyl acrylate, 5 parts by weight of methyl acrylate, a urethane prepolymer obtained by reacting an ethylene oxide propylene oxide adduct of butanol with hexamethylene diisocyanate according to a conventional method and 2-hydroxyethyl. 10 parts by weight of a compound obtained by reacting an acrylate with a urethane reaction was dissolved in 200 parts by weight of methanol, and 2,2′-azobisisobutyronitrile (AIB
N) A reaction liquid obtained by adding 3 parts by weight and reacting at 65 ° C. for 4 hours.

Example 7 A printing film was prepared in the same manner as in Example 1 except that the following diluted reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

2-hydroxyethyl methacrylate 85
Parts by weight, 5 parts by weight of butyl acrylate, 5 parts by weight of butyl methacrylate, 5 parts by weight of the compound represented by the formula (7), and 5 parts by weight of the compound represented by the formula (8). A reaction solution containing a copolymer, which is obtained by dissolving 3 parts by weight of 2,2′-azobisisobutyronitrile (AIBN) in 4 parts by weight and reacting it at 65 ° C. for 4 hours. A diluted reaction liquid obtained by adding to the above, ammonia water in the same molar amount as the addition amount of the compound represented by the above formula (8), and further adding 100 parts by weight of water for dilution.

Comparative Example 1 A printing film was prepared in the same manner as in Example 1 except that the following reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

100 parts by weight of methyl methacrylate was dissolved in 200 parts by weight of ethyl acetate, 3 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was added, and the mixture was heated to 65 ° C.
The reaction solution obtained by reacting for 4 hours.

Comparative Example 2 A printing film was prepared in the same manner as in Example 1 except that the following reaction liquid was used as the surface treatment agent instead of the surface treatment agent in Example 1. The printing film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

2-hydroxyethyl methacrylate 10
0 parts by weight was dissolved in 200 parts by weight of methanol,
A reaction liquid obtained by adding 3 parts by weight of 2′-azobisisobutyronitrile (AIBN) and reacting at 65 ° C. for 4 hours.

Comparative Example 3 10 parts by weight of a 10% aqueous solution of polyvinyl alcohol (PVA-117 manufactured by Kuraray Co., Ltd.) and 10 parts by weight of a slurry containing 20% of porous silica beads having an average particle size of about 10 μm. The surface treatment agent was adjusted by mixing with the parts.

This surface treating agent was applied to a 70 μm thick polyester film of the same type as used in Example 1 with a 50 μ applicator, and the coating was carried out at 100 ° C. for 3 days.
A printing film was obtained by drying for a minute. The printing film was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

(Comparative Example 4) Polyacrylic acid (molecular weight 5
70% by weight of a 30% aqueous solution of 10,000) and 30 parts by weight of polyoxylene oxide (molecular weight 10,000) were used in the same manner as in Comparative Example 3 except that a surface treating agent was used to produce a printing film. Example 1 of the printing film
Evaluation was made in the same manner as in. The results are shown in Table 1.

[0110]

[Table 1]

From the results of the above Examples and Comparative Examples, it can be seen that the surface treating agent of the present invention can modify the surface without impairing the transparency of the object to be treated.
Further, it can be seen that the printing material treated with the surface treatment agent of the present invention has improved affinity for aqueous ink. Therefore, when printing or printing with a water-based ink on the surface of the printing material according to the present invention, a good printing state or a good printing state can be obtained with good adhesion of the water-based ink. Further, even when the surface is treated with a surface treatment agent containing a silane coupling agent, no fingerprints are attached even if the surface is treated, and the handleability is excellent. Further, it can be seen that the printing material treated with the surface treatment agent of the present invention has excellent scratch resistance and good surface characteristics.

(2) Printing Test-Production of Printing Fabrics-Printing pretreatment agent 1a containing 10 g / liter of each of the reaction solutions or reaction diluents in Examples 1 to 7 and Comparative Example 1 or Comparative Example 2 above. To 7a, 8a, 9a, and 20 g / liter of the pretreatment agent for printing 1b to 7
b, 8b, 9b on the surface of polyester cloth under the following conditions [1 dip, 1 nip, 80% squeeze, 2
Drying for 1 minute, heat setting at 160 ° C. for 2 minutes], coating and drying to obtain a polyester textile printing cloth. Further, a nylon printing cloth was obtained in the same manner.

In Table 2, as types of printing cloth, a means polyester printing cloth and nylon printing cloth treated with the printing pretreatment agents 1a to 9a, and b means printing pretreatment agent 1b. 9b refers to polyester and nylon printing fabrics.

Comparative Example 3 was carried out in the same manner as in Example 1 in this printing test except that the printing pretreatment agent was not used.

—Preparation of Printing Paste— Four kinds of printing pastes A to D having the following compositions were prepared.

[Printing Paste A] 70% of fine gum HES (5% aqueous solution, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 30% sorbitose C-5 (5% aqueous solution, manufactured by Matsutani Chemical Co., Ltd.) % Solution containing 50 parts Dye Sumikaron Blue S-BG (Sumitomo Chemical Co., Ltd.) 3 parts Urea ······································································・ 0.3 parts Dense dye (IP Thermos P-26, one hand company Yushi-Seiya Kogyo Co., Ltd.) ・ ・ ・ ・ 2 parts Water ・ ・ ・ ・ ・ ・・ ・ ・ ・ 34.7 parts [Printing paste B] Duck Algin NSP-H (5% aqueous solution, manufactured by Kibun Food Chemifa Co., Ltd.) 50 parts Dye Dianix Navy Blue ER-Fs conc ( Mitsubishi Kasei Hoechst Co., Ltd.・ ・ ・ ・ ・ ・ ・ ・ ・ 3 parts Urea ・ ・ ・ ・ ・ ・ ・ ・ ・ 10 parts Tartaric acid ・ ・ ・・ ・ ・ 0.3 parts Dense agent (IP Thermos P-26, one-sided company Yushi Industrial Co., Ltd.) ・ ・ ・ ・ 2 parts Water ・ ・34.7 parts [Printing paste C] Fine gum HMT (5% aqueous solution, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 50 parts dye Dianix Red A2B-Fs conc (manufactured by Mitsubishi Kasei Hoechst Co., Ltd.) 3 parts urea 10 parts tartaric acid 0.3 parts Thermos P-26, one-sided company Yushi Kogyo Co., Ltd ..・ ・ ・ ・ 34.7 parts [Printing paste D] A solution containing 70% of duck algin NSPH (5% aqueous solution, manufactured by Kibun Food Chemifa Co., Ltd.) and 30% of indalca AGBV (5% aqueous solution, manufactured by Cesarpina)・ ・ ・ ・ ・ ・ ・ 50 parts Dye Sumikaron Cyanine GR (Sumitomo Chemical Co., Ltd.) ・ ・ ・ ・ ・ ・ 3 parts Urea ・ ・ ・ ・ ・ ・・ ・ ・ ・ 5 parts SOLVER 56 (dye dissolving agent, manufactured by Yatsusha Yushi Kogyo Co., Ltd.) ・ ・ ・ 5 parts Ammonium sulfate ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ 2 parts Water ・ ・ ・ ・ ・ ・ ・ ・ 35 parts-Manufacture of printing cloth- Apply one of the printing pastes A to C to the polyester printing cloth described above.
It was printed with 20 mesh gauze, dried at 120 ° C. for 90 seconds, and steamed at 170 ° C. for 7 minutes. Then, under the following water washing conditions [bath ratio 1:20, trypon P-60 at 2 g / liter, hydrosulfite at 2 g / litre, and sodium hydroxide at 2 g / liter at 80 ° C. for 20 minutes]. A polyester textile printing cloth was manufactured by washing with water and drying.

The above printing paste D was printed on the above nylon printing cloth with a 120-mesh gauze, and the mixture was printed at 120 ° C. for 9 minutes.
It was dried for 0 seconds and steamed at 100 ° C. for 30 minutes. Then, the fabric was washed with water under the following washing conditions [bath ratio 1:20, 2 g / l of bisnol RK was treated at 60 ° C. for 20 minutes], and dried to produce a nylon textile printing fabric.

The polyester printing cloth and the nylon printing cloth thus obtained were evaluated for the following items. The results are shown in Table 1.

<Dyeing property> A polyester cloth which has not been treated with a printing pretreatment agent is printed using the above printing pastes A to C, and a nylon cloth which has not been treated with the printing pretreatment agent is used for the above printing. The cloth printed with the paste D was used as a reference cloth. Among these, the dyeing property of the reference cloth printed with the same material as the printing cloth in each example with the same printing paste is 100%,
On the other hand, the dyeing property of the printing cloth in each example is shown in percentage. For example, the dyeing property of the printing cloth of the example is 110.
In the case of%, it means that the dyeing density is 10% higher than that of the reference fabric and the dyeing property is improved.

<Permeability> The printing cloth in each Example was visually observed and the permeability of the dye was evaluated according to the following criteria.

⊚: No dyeing unevenness and high backside dyeing density, ◯: No dyeing unevenness on printed surface, low backing dyeing density, Δ: Slight uneven dyeing on printing surface, X: There is uneven dyeing on the printed surface.

<Sharpness> The printing cloth printed in each example using the pattern for judging sharpness was visually observed and evaluated according to the following criteria. That is, a polyester cloth that has not been treated with a printing pretreatment agent is printed with a pattern for sharpness determination and the printing pastes A to C, and a nylon cloth that has not been treated with the printing pretreatment agent is sharpened. A reference cloth was printed using the pattern for determining the sex and the printing paste D described above. Among these, based on the sharpness of the reference fabric printed with the same printing paste with the same material as the printing fabric in each example, the sharpness of the printing fabric in each example was relatively evaluated by the following criteria. .

◯: Sharpness superior to that of the reference cloth, Δ: Sharpness equivalent to that of the reference cloth, ×: Inferior sharpness to that of the reference cloth, XX The sharpness is remarkably inferior to that of the reference cloth.

[0124]

[Table 2]

From the results of the above-mentioned printing test, when the printing material obtained by treating with the surface treating agent of the present invention is printed with the aqueous dye, the paste of the aqueous dye is good and a good printing state can be obtained. The printing material of the present invention does not easily deteriorate its surface characteristics such as affinity and permeability with an aqueous dye even by washing. Moreover, it can be seen that the printed product of the present invention can stably hold the complicated pattern printed with high sharpness without causing the bleeding of the aqueous dye or the so-called "blinding" phenomenon.

[0126]

EFFECTS OF THE INVENTION According to the present invention, a surface treating agent capable of imparting good water absorption and good affinity to water-based inks and water-based dyes to the surface of a substrate, particularly a hydrophobic substrate made of synthetic polymer or the like. Can be provided.

According to the present invention, it is possible to provide a printing agent and a printing solvent which are excellent in water absorption and printability or printability.

Further, since the surface treating agent of the present invention improves the water absorption of the surface of the hydrophobic substrate, it is possible to impart anti-fogging property to the resin molding, glass, mirror surface and the like.

Claims (8)

[Claims] 1. The following general formula (1): (However, R ¹ represents a hydrogen atom or a methyl group, and R ²
Represents a hydrogen atom or a lower alkyl group. ), And a surface treating agent comprising a copolymer having a monomer capable of radical polymerization having at least two oxyalkylene groups in the molecule. 2. The copolymerization composition according to claim 1, wherein the monomer represented by the chemical formula 1 and the radically polymerizable monomer having at least two oxyalkylene groups in the molecule are contained in the copolymer composition in an amount of 50% by weight or more. The surface treatment agent according to. 3. The radically polymerizable monomer having at least two oxyalkylene groups in the molecule is a monomer having at least two oxyalkylene groups and a polymerizable double bond in the molecule. The surface treatment agent according to 1 or 2. 4. The radically polymerizable monomer having at least 2 mol of an oxyalkylene group in the molecule,
The following general formula (2): (However, R ³ represents a hydrogen atom or a methyl group, and R ⁴
Represents a hydroxyl group, an alkoxy group, a phenoxy group, and a carboxyl group. n is an integer of 2 or more. The surface treatment agent according to claim 1 or 2, which is a monomer represented by the formula (1). 5. The radical-polymerizable monomer having at least 2 mol of oxyalkylene group in the molecule,
The following general formula (3): (However, R ³ represents a hydrogen atom or a methyl group, and R ⁴
Represents a hydroxyl group, an alkoxy group, a phenoxy group, and a carboxyl group, and R ⁵ represents an alkylene group having 1 to 6 carbon atoms.
A represents a structure between NCO groups in the diisocyanate compound. m is an integer of 2 or more. The surface treatment agent according to claim 1 or 2, which is any one of the monomers represented by the formula (1). 6. The radically polymerizable monomer having at least 2 mol of an oxyalkylene group in the molecule,
The monomer obtained by reacting a urethane prepolymer having an NCO terminal obtained by reacting polyoxyethylene glycol and a diisocyanate compound with the acrylate or methacrylate represented by the above Chemical Formula 1. The surface treatment agent according to 1 or 2. 7. A printing material treated with the surface treatment agent according to claim 1. 8. A printing material obtained by treating with the surface treatment agent according to any one of claims 1 to 6.