JP5090076B2 - Additive for coating resin - Google Patents

Description

  The present invention relates to an additive for a coating resin and a coating resin composition.

  In the fields of painting and printing, coating with a coating resin is performed to improve film characteristics or surface characteristics. For example, coating resins are used in paints in the coating field, inks in the printing field, and binders.

  However, in any field, when coating is performed, the coating after drying or curing has a poor antistatic effect, and the coating is charged, causing various troubles due to charging.

  In order to solve such a problem, Patent Document 1 discloses an antistatic material in which a film is applied using a coating material containing a low molecular weight compound containing a sulfonate group, the base component of which is an amine having at least one polyethylene oxide group. An easy-adhesive polyester film having excellent properties is disclosed. However, the sulfonate group-containing low molecular weight compound described in Patent Document 1 has low solubility in organic solvents, and its use is limited to aqueous coating agents.

When the antistatic agent is added to the coating resin composition, it is not preferable to add a dried powdery antistatic agent because the undissolved material remains in the coated film after coating. Addition of an antistatic agent in the form of an aqueous solution is not preferable because it affects the reaction with the curing agent or, in some cases, causes aggregation / coagulation of the resin component. Further, when the coating film is washed with water, the antistatic effect is lowered, and when the coating film is stored under high humidity, whitening occurs.
JP-A-9-141800

  The problem of the present invention is that it is soluble in an organic solvent and can be added to a coating resin in an organic solvent system to give a coating film having a good antistatic property. An object of the present invention is to provide an additive for a coating resin and a coating resin composition that do not decrease and do not whiten even when stored under high humidity.

  The present invention relates to (a) a compound represented by formula (I) (hereinafter referred to as compound (I)), and (b) an additive for coating resin containing an anionic surfactant having radical polymerizability, and this additive And a coating resin composition containing the coating resin.

(In the formula, R is an alkyl or alkenyl group having 4 to 22 carbon atoms, A ¹ is an alkylene group having 2 to 4 carbon atoms, and n is a number of 1 to 30 indicating the average number of moles added of the oxyalkylene group, n A ^{1 s} may be the same or different, and R ¹ , R ² , and R ³ each independently represents an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and at least 1 Is a C 1-3 hydroxyalkyl group.)

  The additive for coating resin of the present invention can obtain a stable coating film, and further, the antistatic effect does not decrease even when the coating film is washed with water, and it does not whiten even when stored under high humidity. Excellent resistance to high humidity storage.

[Additive]
The additive of the present invention contains compound (I) as component (a) and an anionic surfactant having radical polymerizability as component (b).

In compound (I), from the viewpoint of organic solvent solubility, R represents an alkyl group or alkenyl group having 4 to 22 carbon atoms, preferably an alkyl group having 8 to 22 carbon atoms, and an alkyl group having 8 to 18 carbon atoms. Is more preferable, and an alkyl group having 8 to 12 carbon atoms is still more preferable. A branched alkyl group having 8 to 12 carbon atoms is particularly preferable. From the viewpoint of antistatic properties and organic solvent solubility, A ¹ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group. From the viewpoint of antistatic properties and organic solvent solubility, n is a number of 1 to 30 indicating the average number of added moles of the oxyalkylene group, preferably 1 to 20, more preferably 1 to 10. A number of ˜5 is more preferred. R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and at least one is a hydroxyalkyl group having 1 to 3 carbon atoms. From the viewpoint of antistatic properties and organic solvent solubility, it is preferred that all of R ¹ , R ² and R ³ are hydroxyethyl groups.

  Compound (I) can be used alone or in combination.

  The production method of the compound (I) of the present invention is not particularly limited. For example, triethanolamine or the like obtained by addition reaction of an alcohol having an oxyalkylene group (alkylene group having 2 to 4 carbon atoms) and chlorosulfonic acid can be used. Can be obtained by neutralization.

  The component (b) of the present invention is not particularly limited as long as it is an anionic surfactant having radical polymerizability, and examples thereof include a compound represented by the formula (II) (hereinafter referred to as compound (II)).

[Wherein, R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and R ⁷ has an alkylene group having 1 to 4 carbon atoms or an alkyl group having 1 to 18 carbon atoms as a substituent. An arylene group, A ² may be an alkylene group having 2 to 18 carbon atoms, or —CH ₂ CH (CH ₂ OR ⁸ ) — (R ⁸ may be an alkyl group having 1 to 18 carbon atoms, or a substituent group having 1 to 18 carbon atoms. Aryl group optionally having an alkyl group), m is a number from 1 to 200 indicating the average number of moles added of the A ² O group, and m A ² are the same or different. May be. M represents a cation. ]

In the compound (II), R ⁴ and R ⁵ are preferably a hydrogen atom and R ⁶ is a hydrogen atom or a methyl group, particularly a methyl group, from the viewpoint of antistatic properties after washing with water and high humidity storage stability. R ⁷ is preferably an alkylene group having 1 to 4 carbon atoms or a phenylene group having an alkyl group having 4 to 18 carbon atoms as a substituent from the viewpoint of antistatic properties after washing with water and high humidity storage stability, 4 alkylene group is more preferable, C1-C2 alkylene group is still more preferable, and ethylene group is especially preferable. A ² represents an alkylene group having 4 to 18 carbon atoms or —CH ₂ CH (CH ₂ OR ⁸ ) — (R ⁸ has 1 to 18 carbon atoms) from the viewpoint of antistatic properties after washing with water and high humidity storage stability. A phenyl group having an alkyl group having 4 to 18 carbon atoms as an alkyl group or a substituent, preferably a group having 1 to 18 carbon atoms, and more preferably an alkyl group having 4 to 18 carbon atoms, and 2 to 3 carbon atoms. A mixed group with an alkylene group is preferred. The alkylene group having 4 to 18 carbon atoms may be linear or branched, and examples thereof include groups such as ethylethylene, dimethylethylene, butylethylene, octylethylene, decylethylene, dodecylethylene, tetradecylethylene, and hexadecylethylene. It is done. R ⁸ in the group represented by —CH ₂ CH (CH ₂ OR ⁸ ) — is preferably an alkyl group having 1 to 18 carbon atoms, but may be linear or branched. For example, a methyl group or an ethyl group Propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. The alkylene group having 2 to 3 carbon atoms may be a straight chain or a branched chain, and examples thereof include an ethylene group and a propylene group. The antistatic property after washing with water, high humidity storage resistance, and the phase with the component (a) From the viewpoint of solubility, an ethylene group is preferred. m is a number from 1 to 200 indicating the average number of moles added of the A ² O group, but from the viewpoint of antistatic properties after washing with water and high humidity storage stability, the number from 1 to 150 is preferable, and from 1 to 100 A number is more preferable, and a number of 1 to 50 is still more preferable.

  Examples of the cation represented by M include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, and ammonium substituted with an alkyl group having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms. Examples include ammonium ions of trialkanolamines having a hydroxyalkyl group having 1 to 3 carbon atoms such as ions and triethanolamine. From the viewpoint of compatibility with the component (a), ammonium ions, alkyl-substituted ammonium ions, Ammonium ion of trialkanolamine is preferable, and ammonium ion and ammonium ion of triethanolamine are more preferable.

  Examples of the compound (II) include compounds represented by the following formulas (II-1) to (II-5), antistatic properties after washing with water, high humidity storage resistance, and compatibility with the component (a). In view of the above, compounds represented by formulas (II-1) to (II-3) are preferred, and a compound represented by formula (II-1) is more preferred.

[Wherein R ⁴ , R ⁵ , R ⁶ , m and M have the above-mentioned meanings. R ⁷¹ is an alkylene group having 1 to 4 carbon atoms, A ²¹ represents an alkylene group having 2 to 4 carbon atoms, m pieces of A ²¹ may be the same or different. ]

[Wherein R ⁴ , R ⁵ , R ⁶ and M have the above-mentioned meanings. R ⁷² is an alkylene group having 1 to 4 carbon atoms, A ²² is a group represented by —CH ₂ CH (CH ₂ OR ⁸¹ ) — (R ⁸¹ represents an alkyl group having 1 to 18 carbon atoms), and A ²³ is alkylene group having 2 to 4 carbon atoms, m ₁ is the number of 1 to 150 showing an average addition mole number of a ²³ O group, m ₁ pieces of a ²³ may be the same or different. ]

[Wherein R ⁴ , R ⁵ , R ⁶ and M have the above-mentioned meanings. R ⁷³ is an alkylene group having 1 to 4 carbon atoms, A ²⁴ is a group represented by —CH ₂ CH (R ⁹ ) — (R ⁹ is an alkyl group having 3 to 16 carbon atoms), and A ²⁵ is a carbon number. 2-4 alkylene group, m ₂ is the number of 1 to 150 showing an average addition molar number of a ²⁵ O group, m ₂ pieces of a ²⁵ may be the same or different. ]

[Wherein R ⁴ , R ⁵ , R ⁶ and M have the above-mentioned meanings. R ⁷⁴ is an alkylene group having 1 to 4 carbon atoms, A ²⁶ is —CH ₂ CH (CH ₂ OR ⁸² ) — (R ⁸² is an aryl group optionally having an alkyl group having 1 to 18 carbon atoms as a substituent. A ²⁷ is an alkylene group having 2 to 4 carbon atoms, m ₃ is a number of 1 to 150 indicating the average added mole number of the A ²⁷ O group, and m ₃ A ²⁷ is It may be the same or different. ]

[Wherein R ⁴ , R ⁵ , R ⁶ , m and M have the above-mentioned meanings. R ⁷⁵ represents an arylene group which may have an alkyl group having 1 to 18 carbon atoms as a substituent, A ²⁸ represents an alkylene group having 2 to 4 carbon atoms, and m A ²⁸ may be the same or different. good. ]

  Among the compounds represented by the formula (II-1), the compound represented by the formula (II-1-1) is more preferable.

[Wherein R ⁴ , R ⁵ , R ⁶ , R ⁷¹ and M have the above-mentioned meanings. A ²⁹ represents an alkylene group having 4 carbon atoms, A ³⁰ represents an alkylene group having 2 to 3 carbon atoms, m ₄ represents a number of 0 to 50 indicating the average number of moles added of the A ²⁹ O group, and m ₅ represents A ³⁰ O. is the number of 1 to 150 showing an average addition mole number of groups, m ₄ + m ₅ is a number from 1 to 200. Further, m ₅ A ³⁰ may be the same or different. ]

In the general formula (II-1-1), A ³⁰ is preferably an ethylene group from the viewpoint of antistatic properties after washing with water, high humidity storage resistance and compatibility with the component (a).

In the general formula (II-1-1), m ₄ is a number from 0 to 50 indicating the average number of moles added of the A ²⁹ O group, and antistatic property after washing with water, high humidity storage resistance, and (a) The number of 0-10 is preferable from a compatible viewpoint with a component. Although m ₅ is a number of from 1 to 150 showing an average addition molar number of A ³⁰ O group, antistatic after washing with water, from the viewpoint of compatibility with the anti-high humidity storage properties and component (a), 1 A number of 50 is preferred, and a number of 1 to 40 is more preferred.

  In the present invention, the component (b) can be used alone or in combination. As the component (b) of the present invention, a commercially available product can be used, but it can also be produced by a known method.

  Compound (II) is, for example, one or two compounds such as alkylene oxide, alkyl glycidyl ether or α-olefin epoxide in the presence of a catalyst in unsaturated alcohol such as 3-methyl-3-buten-1-ol and allyl alcohol. The above is added to obtain ether alcohol, which is obtained by sulfating with a sulfating agent and neutralizing with a basic substance such as triethanolamine. Examples of the sulfating agent include chlorosulfonic acid, anhydrous sulfuric acid and amidosulfuric acid. Amidosulfuric acid is used from the viewpoint of reducing side reactions such as addition reaction of sulfuric acid group to double bond group and isomerization of double bond group Is preferred.

  The additive for coating resin of the present invention exhibits a particularly remarkable effect by the combined use of the component (a) and the component (b). The reason why such a remarkable effect is manifested is not clear, but by incorporating the component (b) of the present invention into the resin, the compatibility between the resin and the component (a) is improved, and (a) In order to improve the dispersibility of the component in the resin, the whitening property of the resin composition under high humidity is suppressed, and as a result of the interaction between the component (b) and the component (a), the resin composition is washed with water. Are likely to remain in the resin, and the antistatic effect is unlikely to decrease.

  In addition to the components (a) and (b), the additive of the present invention comprises an unreacted component in the production of the components (a) and (b) and an antistatic agent having high solubility in organic solvents other than the component (a). An agent can be contained. As such other antistatic agents, from the viewpoint of improving the water resistance of the coating resin composition, polyoxyalkylene (alkylene having 2 to 4 carbon atoms and an average addition mole number of oxyalkylene groups of 1 to 20). Alkyl (alkyl group having 8 to 22 carbon atoms) potassium phosphate, at least one selected from the group consisting of diglycerin and esters of fatty acids having 8 to 22 carbon atoms and sorbitan and esters of fatty acids having 8 to 22 carbon atoms (Hereinafter referred to as component (c)) is preferred.

  Examples of potassium polyoxyalkylene alkyl phosphate include a compound represented by formula (III) (hereinafter referred to as compound (III)).

(Where R ¹¹ is the formula

R ¹² represents a group represented by the formula

The group represented by these is shown. Here, R ¹³ is an alkyl group having 8 to 22 carbon atoms, A ⁵ is an alkylene group having 2 to 4 carbon atoms, and p is a number of 1 to 20 indicating the average number of moles added of the oxyalkylene group. )
In compound (III), from the viewpoint of organic solvent solubility and water resistance, R ¹³ represents an alkyl group having 8 to 22 carbon atoms, preferably an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 8 to 12 carbon atoms. Groups are more preferred. A ⁵ is an alkylene group having 2 to 4 carbon atoms, and an ethylene group is preferable from the viewpoint of the effect of the present invention. From the viewpoint of organic solvent solubility and water resistance, p is a number of 1 to 20 indicating the average number of added moles of the oxyalkylene group, preferably 1 to 10, and more preferably 1 to 5.

  Polyoxyalkylene alkyl potassium potassium can be obtained by reacting polyoxyalkylene alkyl alcohol with phosphorus pentoxide to give polyoxyalkylene alkyl phosphate and neutralizing with potassium hydroxide. In order to keep the by-product potassium phosphate low, the molar ratio of polyoxyalkylene alkyl alcohol to phosphorus pentoxide is preferably 3.2 mol of polyoxyalkylene alkyl alcohol per mol of phosphorus pentoxide.

  As an ester of diglycerin and a fatty acid having 8 to 22 carbon atoms, from the viewpoint of organic solvent solubility and water resistance, 1 mol of diglycerin and 1 to 2 moles of fatty acid having 8 to 22 carbon atoms, especially 8 to 18 carbon atoms. The esters are preferred.

  Esters of diglycerin and fatty acids having 8 to 22 carbon atoms are obtained by dehydrating esterification of diglycerin and fatty acids having 8 to 22 carbon atoms at about 220 ° C. for about 4 to 5 hours under a nitrogen seal. Can do. The diglycerin (glycerin 2 molar condensate) in the diglycerin is preferably 50% or more, more preferably 70% or more, from the viewpoint of organic solvent solubility and water resistance.

  Moreover, as ester of sorbitan and a C8-C22 fatty acid, from a viewpoint of organic solvent solubility and water resistance, 1 mol of sorbitan, C1-28, especially 1-28 fatty acids of 8-18 carbon atoms, The esters are preferred. Esters of sorbitan and fatty acids having 8 to 22 carbon atoms can be obtained by dehydrating esterification of sorbitan and fatty acids having 8 to 22 carbon atoms at about 230 ° C. for about 4 to 5 hours.

  The content of the component (a) in the additive of the present invention is preferably 10 to 80% by weight, more preferably 40 to 80% by weight, from the viewpoint of achieving the object of the present invention. The content of component (b) is preferably 10 to 80% by weight, more preferably 20 to 50% by weight, from the viewpoint of achieving the object of the present invention. In the additive of the present invention, the content ratio of the component (a) and the component (b) is (a) / (b) (weight ratio) from the viewpoint of antistatic properties after washing with water and resistance to whitening under high humidity storage. ) = 80/20 to 20/80 is preferable, 80/20 to 40/60 is more preferable, and 75/25 to 50/50 is still more preferable.

  In addition, the content of the component (c) when the component (c) is contained in the additive of the present invention is preferably 2 to 80% by weight from the viewpoint of water resistance of the coating resin composition, and is preferably 4 to 75. Weight percent is more preferred.

[Coating resin composition]
The coating resin composition of the present invention contains the additive of the present invention and a coating resin. The content of the additive of the present invention is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the coating resin, from the viewpoints of organic solvent solubility, antistatic properties after washing with water, and high humidity storage stability. Preferably it is 1-10 weight part, More preferably, it is 2-5 weight part.

  The coating resin used in the present invention is not particularly limited as long as it is a resin suitable for use in coating a base material, for example, as an ink, paint, binder, etc. Resin, polyamide resin, epoxy resin, polyurethane resin and the like. In addition, a resin such as a thermosetting type in which the film is cured with a diisocyanate compound and a UV curable type in which the film is cured by UV irradiation may be used. Among these coating resins, acrylic resins and polyamide resins are preferable from the viewpoint of maintaining transparency.

  The content of the coating resin in the coating resin composition of the present invention is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, from the viewpoint of achieving the object of the present invention.

  The coating resin composition of the present invention preferably further contains an organic solvent. Although it does not specifically limit as an organic solvent, Aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, etc. can be used. Among these, toluene, methyl ethyl ketone, methyl isobutyl ketone, normal hexane, n-butyl acetate, n-ethyl acetate, and isopropyl alcohol are preferable.

  The content of the organic solvent in the composition of the present invention is preferably 45 to 85% by weight, more preferably 40 to 70% by weight, from the viewpoint of coatability.

  There is no limitation on the method of adding the additive of the present invention, and good performance can be obtained whether it is added before the monomer polymerization reaction constituting the coating resin or added to the coating liquid composition used after polymerization. be able to.

  Although the composition of the present invention can contain water, the content of water in the coating resin composition is preferably less than 5% by weight from the viewpoint of suppressing deterioration of coating film properties such as coating film strength and transparency. It is more preferably less than 1% by weight, and it is preferable that it does not substantially contain.

  In addition to the above components, the coating resin composition of the present invention is generally filled with curing agents such as diisocyanate compounds, pigments / dyes, beads such as glass beads, polymer beads, inorganic beads, and inorganic fillers such as calcium carbonate and talc. Additives such as materials, lubricants, stabilizers, ultraviolet absorbers, polymerization initiators such as peroxides can be blended.

  The coating resin composition of the present invention is a resin composition that can be applied to a substrate to express various functions. For example, a combination of polymer beads, resin, and organic solvent is used as a light diffusion film. A combination of a functional and adhesive resin and an organic solvent functions as an adhesive film, and a combination of a pigment, a resin and an organic solvent exhibits a function as a paint.

The surface specific resistance value after washing of the coating resin composition of the present invention is preferably 1 × 10 ¹³ Ω or less from the viewpoint of maintaining antistatic properties after washing with water. The surface specific resistance value can be measured according to the method described in the examples.

The components in the additive of the present invention and the comparative additive used in the following examples are collectively shown below. The component (a) was dehydrated and solvent-replaced with EDG (diethylene glycol monoethyl ether) in advance and adjusted to an effective content of 50%.
In the following agents, POE (n) represents a polyoxyethylene chain having an average addition mole number n of oxyethylene groups, and POB (n) is a polyoxyethylene having an average addition mole number n of oxybutylene groups. Indicates a butylene chain.

<(A) component>
Compound (a-1): POE (3) Lauryl sulfate triethanolamine salt (50% effective EDG solution)

<(B) component>
Compound (b-1): POB (6) POE (15) 3-methyl-3-butenyl ether sulfate triethanolamine salt (POB (6) and POE (15) are in a block bond)
Compound (b-2): POE (40) ammonium salt of 3-methyl-3-butenyl ether sulfate Compound (b-3): POB (6) POE (5) 3-methyl-3-butenyl ether sulfate Triethanolamine salt (POB (6) and POE (5) are block-bonded)

Examples 1-5 and Comparative Examples 1-3
As coating resin, acrylic resin (Acridic A-801 manufactured by Dainippon Ink & Chemicals, Inc., solid content concentration 50%, solvent toluene / n-butyl acetate, hydroxyl value 50), and hexamethylene diisocyanate (as a curing agent) HMDI), isopropyl alcohol as a coating solvent, and an additive having a composition shown in Table 1 as an additive were used to prepare a coating resin composition having a composition shown in Table 1.

  The obtained coating resin composition was applied to a 100 μm PET biaxially stretched film using a 20 μm applicator, dried, and allowed to stand in a dryer at 50 ° C. for 12 hours to be cured. About the coating film after hardening, the antistatic property (before water washing and after water washing) of a coating film and high-humidity storage stability were evaluated by the following method. The results are shown in Table 1.

<Antistatic evaluation method>
About the coating film after hardening, in the room | chamber interior adjusted to 25 degreeC and relative humidity 50%, the surface specific resistance value was measured with the A-4329 type high resistance meter (Yokogawa YP company). In addition, the cured coating film was scrubbed by hand 10 times under running water, dried, and then adjusted to 25 ° C. and humidity 50% in the same manner using an A-4329 type high resistance meter. Specific resistance values were measured (it can be said that those having a surface specific resistance value of 1 × 10 ¹³ Ω or less have an antistatic effect).

<Method for evaluating high-humidity storage stability>
Tap water with a thickness of about 2 cm is placed in the bottom of a glass container (length 10 cm, width 25 cm, depth 25 cm), and a coating film (applied to the above-mentioned 100 μm PET biaxially stretched film using a 20 μm applicator) on the inner wall of the container The film was made into a size of 5 cm × 10 cm) without being in contact with water, and was tested at 35 ° C. for 7 days while keeping the sealed state. The film taken out from the container was air-dried and then measured for haze using a haze meter.

Claims (3)

(A) Additive for coating resin containing a compound represented by formula (I) and (b) an anionic surfactant having radical polymerizability represented by formula (II) .

(Wherein, R is an alkyl group having 8 to 12 carbon atoms, A ¹ is ethylene group, n represents Ru number der 1-5 showing the average addition molar number of oxyethylene groups .R ^1, R ^2, R ³ Are all hydroxyethyl groups.)

Wherein R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, R ⁷ is an alkylene group having 1 to 4 carbon atoms, A ² is an alkylene group having 2 to 4 carbon atoms, and m is A ² is a number from 1 to 50 indicating the average number of moles added of the O group, and m A ² may be the same or different. M represents an ammonium ion or an ammonium ion of triethanolamine.) The additive for a coating resin according to claim 1 , wherein the content ratio of the component (a) and the component (b) is (a) / (b) (weight ratio) = 80/20 to 20/80. A coating resin composition comprising the additive according to claim 1 or 2 and a coating resin .