JP2013166830A - Surfactant, its production method and aqueous coating agent composition containing the surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surfactant exerting high surface tension depressing ability (dynamic surface tension depressing ability, static surface tension depressing ability).SOLUTION: A surfactant is used which comprises a silicone modified body obtained by chemical reaction of active hydrogen-containing modified silicone and a glycidyl compound expressed by formula (1): {E(-OA)}-Q-{(AO-)H}, wherein: E is a glycidyl group; H is a hydrogen atom; Q is a reaction residue in which hydrogen atoms are removed from t pieces of primary hydroxy groups of a nonreducible di- or trisaccharide; OA and AO are each a 2-4C oxyalkylene group; n denotes an integer of 1 to 40; t denotes an integer of 2 to 4; p denotes an integer of 1 to 3 (provided that t≥p). The total number of oxyalkylene groups in the glycidyl compound is 10-80.

Description

  The present invention relates to a surfactant, a method for producing the same, and an aqueous coating agent composition containing the same.

In recent years, printers for office automation equipment such as personal computers have been mainly ink jet printing capable of high-speed operation, which includes excellent dynamic and static surface tension as well as high wettability, leveling properties, and permeability. There is a demand for reducing ability. In such applications, modified silicones such as polyether-modified silicones have excellent leveling properties, wettability, dispersibility, etc., but their dynamic surface tension reducing ability is not at a satisfactory level.
In addition, in the use of coating agents such as inks, modified silicones have tended to be avoided in the past because they have low reliability with respect to repelling, pinholes and the like in addition to the above-mentioned drawbacks.
Further, in the fields such as high-speed printing, printing requiring high-speed coating, and paper industry, there are the same needs as described above, but they are still insufficient.

  In response to the above needs, a surfactant composition (Patent Document 1) obtained by blending an ethoxylated acetylene glycol with a silicone surfactant has been proposed.

JP 2005-103457 A

The surfactant composition described in Patent Document 1 is a combination of a component having excellent leveling properties (silicone surfactant) and a component having excellent dynamic surface tension reducing ability (ethoxylated acetylene glycol). The obtained performance does not greatly exceed the intermediate level of the performance of each of the blended components, and there is a problem in the dynamic surface tension lowering ability, etc., and the above-mentioned needs have not been sufficiently met. .
That is, an object of the present invention is to provide a surfactant that exhibits high surface tension reducing ability (dynamic surface tension reducing ability, static surface tension reducing ability).

The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems.
That is, the surfactant of the present invention is characterized by a modified silicone (Y) obtained by chemically reacting an active hydrogen-containing modified silicone (S) with a glycidyl compound (G) represented by the general formula (1). ).

_{{E (-OA) n} p} -Q - {(AO-) n H} t-p (1)

  In general formula (1), E is a glycidyl (1,2-epoxypropyl) group, H is a hydrogen atom, Q is a reaction in which a hydrogen atom is removed from t primary hydroxyl groups of a non-reducing di- or trisaccharide. Residues, OA and AO (hereinafter collectively referred to as AO) are oxyalkylene groups having 2 to 4 carbon atoms, n is an integer of 1 to 40, t is an integer of 2 to 4, and p is an integer of 1 to 3 (Where t ≧ p), and the total number of AO in the general formula (1) is 10-80.

A feature of the method for producing the surfactant of the present invention is a method for producing the above surfactant,
The process includes a step of chemically reacting the active hydrogen-containing modified silicone (S) and the glycidyl compound (G) represented by the general formula (1) to obtain a silicone-modified product (Y) without a reaction solvent and a reaction catalyst. Is the gist.

  The water-based coating composition of the present invention is characterized by comprising a water-based coating agent and the above-mentioned surfactant, and containing 0.1 to 5% by weight of this surfactant based on the weight of the water-based coating agent. Is the gist.

The surfactant of the present invention exhibits high surface tension reducing ability (dynamic surface tension reducing ability, static surface tension reducing ability).
According to the method for producing a surfactant of the present invention, the above surfactant can be easily prepared.
Since the coating agent composition of the present invention contains an aqueous coating agent and the above surfactant, the surface tension (dynamic surface tension, static surface tension) is sufficiently low.

It is a graph showing the result of having measured dynamic surface tension about surfactant (Y3) obtained in Example 3, and comparative surfactant (HY1)-(HY3) obtained in Comparative Examples 1-3.

<Active hydrogen-containing modified silicone (S)>
The active hydrogen-containing modified silicone (S) includes a hydroxyl group-containing polyether-modified silicone (S1), an amino group-containing amino-modified silicone (S2), a carboxy group-containing carboxy-modified silicone (S3), and a hydroxyl group-containing carbinol-modified silicone (S4). And at least one selected from the group consisting of a phenolic hydroxyl group-containing phenol-modified silicone (S5) and a mercapto group-containing mercapto-modified silicone (S6).

  The active hydrogen-containing modified silicone (S) can be classified into a side chain type, a both-end type, and a one-end type depending on the modification position of the silicone, and any of these can be used, but the side chain type is preferred.

  The hydroxyl group-containing polyether-modified silicone (S1) is a polyether-modified silicone containing a polyether-derived hydroxyl group, which can be easily obtained from the market, and examples thereof include the following products.

  Side chain types include KF-351A, KF-353, KF-354L, KF-615A, KF-640, KF-945, KF-6011, KF-6015, KF-6020, and X-22-2516 (and above) FZ2110, FZ2120, FZ2130, FZ2161, FZ2166, FZ2191, FZ7001, FZ7002, SF8428, SH3771, BY16-027 and BY16-036 (above, manufactured by Toray Dow Corning Silicone); TSF4440 , TSF4441, TSF4445, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials LLC); SN-WET123, SN-WET125 (manufactured by San Nopco Co., Ltd.), and the like.

  Examples of both terminal types include X-22-4952 (manufactured by Shin-Etsu Chemical Co., Ltd.); FZ2203 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like. Examples of one terminal type include FZ2122 (Toray Dow). Corning Silicone Co., Ltd.).

  These hydroxyl group-containing polyether-modified silicones have a wide cloud point (1% by weight aqueous solution method, initial turbid point), but for example, when emphasizing wettability, those having a cloud point of 30 to 90 ° C., defoaming properties When emphasizing the permeability, it is more effective to select one having a cloud point of 5 to 50 ° C.

  The amino group-containing amino-modified silicone (S2) is a modified silicone containing an amino group derived from a monoamine or diamine and can be easily obtained from the market. Examples thereof include the following products.

  As side chain types, KF868, KF880, KF8002 and X-22-3820W etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.); FZ3504, FZ3705, FZ3760, SF8417, BY16-850, BY16-850 and BY16-890 (above , Manufactured by Toray Dow Corning Silicone Co., Ltd.); TSF4702, TSF4704 and TSF4706 (manufactured by Momentive Performance Materials LLC).

  Examples of both end types include KF8010 and PAM-E (and above, manufactured by Shin-Etsu Chemical Co., Ltd.), etc., and examples of single end types include TSF4700 and TSF4701 (and above, manufactured by Momentive Performance Materials LLC). Can be mentioned.

  The carboxy group-containing carboxy-modified silicone (S3) is a modified silicone containing a carboxy group derived from a carboxylic acid, and can be easily obtained from the market. Examples thereof include the following products.

  Examples of the side chain type include X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd.); BY16-880 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like, and examples of both end types include X-22-162C and the like. (Manufactured by Shin-Etsu Chemical Co., Ltd.); BY16-750 (manufactured by Toray Dow Corning Silicone Co., Ltd.); TSF4770 (manufactured by Momentive Performance Materials LLC) and the like.

  The hydroxyl group-containing carbinol-modified silicone (S4) is a modified silicone containing a hydroxyl group derived from alcohol and can be easily obtained from the market. Examples thereof include the following products.

  As side chain types, X-22-4015, X-22-4039 and the like (manufactured by Shin-Etsu Chemical Co., Ltd.); SF8428 (manufactured by Toray Dow Corning Silicone Co., Ltd.); TSF4750 (Momentive Performance Materials Joint) As a double-ended type, X-22-160AS and KF-6001 (and above, manufactured by Shin-Etsu Chemical Co., Ltd.); BY16-201 and SF8427 (and above, Toray Dow Corning Silicone Co., Ltd.) Company-made); TSF4751 (made by Momentive Performance Materials GK) and the like.

  The phenolic hydroxyl group-containing phenol-modified silicone (S5) is a modified silicone containing a hydroxyl group derived from phenol. For example, the following products (both end types) can be easily obtained from the market.

  X-22-1821 (manufactured by Shin-Etsu Chemical Co., Ltd.); BY16-799, BY16-150S, etc. (above, manufactured by Toray Dow Corning Silicone Co., Ltd.).

  The mercapto group-containing mercapto-modified silicone (S6) is a modified silicone containing a mercapto group derived from thioalcohol and can be easily obtained from the market. Examples thereof include the following products.

  Examples of the side chain type include KF-2001 and KF-2004 and the like (manufactured by Shin-Etsu Chemical Co., Ltd.); BX16-838A (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like. X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

<Glycidyl compound (G) represented by general formula (1)>
In the general formula (1), the di- or trisaccharide capable of constituting the reaction residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide is sucrose (saccharose). ), Trehalose, isotrehalose, isosaccharose, gentianose, raffinose, meretitol, planteose and the like. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of water resistance and the like, more preferably sucrose and raffinose, and sucrose is particularly preferable from the viewpoint of supply ability and cost.

  In the general formula (1), examples of the oxyalkylene group (AO) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Of these, oxypropylene and oxybutylene are preferred from the viewpoint of the ability to reduce surface tension. The n AOs may be the same or different, and a plurality of (-OA) n and (AO-) n {hereinafter, these are collectively abbreviated as (AO-) n. } May be the same or different.

  When (AO-) n contains a plurality of types of oxyalkylene groups, the bonding order (block, random and combinations thereof) and content of these oxyalkylene groups are not limited, but block or block It is preferable to include a combination of a shape and a random shape.

  When (AO-) n contains a plurality of types of oxyalkylene groups and oxyethylene is contained, the content ratio (mol%) of the oxyethylene groups is the total of oxyalkylene groups from the viewpoint of surface tension reducing ability and water resistance. Based on the number of moles, 1 to 30 is preferable, 1 to 25 is more preferable, 3 to 25 is particularly preferable, and 3 to 20 is most preferable.

  When (AO-) n contains an oxyethylene group and an oxypropylene group and / or oxybutylene group, from the viewpoint of water resistance, oxypropylene or / and oxybutylene is present at the end away from the reaction residue (Q). Is preferably located. That is, when (AO-) n contains an oxyethylene group and an oxypropylene group and / or oxybutylene group, it is preferable that the oxyethylene group is directly bonded to the reaction residue (Q).

  n is an integer of 1 to 40, preferably an integer of 2 to 37, more preferably an integer of 2 to 33, and particularly preferably an integer of 3 to 30. Within this range, the surface tension reducing ability and the like are further improved. A plurality of n may be different or the same.

  The total number of oxyalkylene groups (AO) in the glycidyl compound (G) represented by the general formula (1) is preferably an integer of 10 to 80, more preferably an integer of 10 to 70, particularly preferably 20 to 70. An integer, most preferably an integer of 20-60. Within this range, the surface tension reducing ability is further improved.

t is an integer of 2 to 4, and is, for example, 3 for sucrose, 2 for trehalose, and 4 for meletitose.
p is an integer of 1 to 3.
However, the value of t is not less than the value of p. That is, t ≧ p.

  For example, an equimolar mixture of a compound having p = 1 and a compound having p = 2 is apparently p = 1.5, but even in this case, the mixture is included in the present invention. . Thus, in the case of a mixture, p is not an integer but can be represented by a real number, and the real number (P ″) is preferably 1.2 to 2.5, more preferably 1.2 to 2, particularly preferably. In this range, the surface tension reducing ability is further improved.

  In the chemical reaction between the active hydrogen-containing modified silicone (S) and the glycidyl compound (G), the amount (% by weight) of the glycidyl compound (G) used is 10 to 10 based on the weight of the active hydrogen-containing modified silicone (S). 200 is preferable, more preferably 10 to 150, particularly preferably 20 to 150, and most preferably 20 to 100. Within this range, the surface tension reducing ability is further improved.

When the amount of the glycidyl compound (G) used is expressed in mol parts, it is as follows. However, when the quantitative relationship between the wt% and the mol parts is inconsequential, the wt% is prioritized.
As for the usage-amount (mol part) of a glycidyl compound (G), 0.1-1.5 are preferable with respect to 1 mol part of active hydrogen of active hydrogen containing modified silicone (S), More preferably, it is 0.1-1.4. Particularly preferred is 0.3 to 1, and most preferred is 0.3 to 0.8. Within this range, the surface tension reducing ability is further improved.

The following compounds etc. are mentioned as a glycidyl compound represented by General formula (1).
“P” represents an oxypropylene group, “E” represents an oxyethylene group, and “B” represents an oxybutylene group, and these subscripts (numbers) represent the number of each. “Q1” is a reaction residue obtained by removing three primary hydroxyl group hydrogen atoms from sucrose, “Q2” is a reaction residue obtained by removing two primary hydroxyl group hydrogen atoms from trehalose, and “Q3” is The reaction residue obtained by removing the hydrogen atoms of the four primary hydroxyl groups from meretitol, “•” means that oxyalkylenes before and after this • are bonded together in a random manner {for example, (−P5 • B5) is oxy That five propylene groups and five oxybutylene groups are bonded in a random manner}, “/” indicates that oxyalkylenes before and after this / are sequentially bonded in a block shape {for example, (−P20 / B5) represents that 20 oxypropylene groups and then 5 oxybutylene groups are bonded}.

  Of these, No. The compound represented by 1-1, 3-1, 4-2, 6-1, 8-1, 13-2, 16-1, 18-2, 24-1 or 25-1 is preferable, and more preferably No. It is a compound represented by 4-2, 6-1, 8-1, 13-2 or 24-1.

  The glycidyl compound (G) represented by the general formula (1) can be obtained by a chemical reaction between the polyether compound (GP) represented by the general formula (2) and epihalohydrin (GE).

Q-{(AO-) _n H} _t (2)

  In the general formula (2), H, Q, t, AO, and n are the same as those in the general formula (1), and the preferred ranges are also the same. The total number of oxyalkylene groups (AO) in the polyether compound represented by the general formula (2) is preferably an integer of 10 to 80, more preferably an integer of 10 to 70, particularly preferably an integer of 20 to 70. Most preferably, it is an integer of 20 to 60. Within this range, the surface tension reducing ability is further improved.

  Epihalohydrin (GE) includes epichlorohydrin, epibromohydrin, and the like. Of these, epichlorohydrin is preferred.

  The amount of the polyether compound (GP) and epihalohydrin (GE) used is preferably such that the polyether compound (GP) / epihalohydrin (GE) molar ratio is 0.25 to 1, more preferably 0.33 to 1. This is the amount. If it is this ratio, the desalting filtration process mentioned later can be implemented simply.

As a method for producing a glycidyl compound (G) by a chemical reaction between a polyether compound (GP) represented by the general formula (2) and an epihalohydrin (GE), poly (polysiloxane) in the presence of an alkali metal hydroxide (A) In a production method for obtaining a glycidyl compound (G) by reacting an ether compound (GP) with an epihalohydrin (GE),
Reaction step (1) in which the water content is adjusted to 2 to 5% by weight based on the weights of the alkali metal hydroxide (A), the polyether compound (GP) and the epihalohydrin (GE), and this reaction is started. It is preferable to contain.

  According to the production method including such a reaction step (1), granulation of the by-product neutralized salt can be promoted and the neutralized salt particles can be increased, and therefore, desalting can be performed by a simple filtration step. Therefore, according to such a manufacturing method, a special water washing treatment apparatus is not required, and a huge amount of drainage is not generated by the water washing treatment, and an advantage in terms of environment and cost can be obtained. In addition, such a manufacturing method does not require an acid catalyst, and therefore, it is not necessary to consider corrosion of manufacturing equipment. Furthermore, since the content of halogen atoms (chlorine atoms, etc.) in the glycidyl compound (G) obtained by such a production method is at a level that does not affect the rust prevention surface, there is no problem in the fields of electronics, electricity, paints, etc. Can be used.

  Examples of the alkali metal hydroxide (A) include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable from the viewpoint of granulation of neutralized salt (increase in particles).

  The amount of the alkali metal hydroxide (A) used is such that the ratio of {base equivalent of the alkali metal hydroxide (A) (eq.) / Equivalent of the halogen of the epihalohydrin (GE) (eq.)} Is 0.7 to An amount of 1.1 is preferable, and an amount of 0.8 to 1.0 is more preferable. With this ratio, the neutralization step of excess alkali metal hydroxide (A) can be omitted, and excess epihalohydrin (GE) can be removed by a dehydration step under reduced pressure or the like.

  The polyether compound (GP) represented by the general formula (2) can be produced by applying a known chemical reaction, for example, 1 mol part of a non-reducing di- or trisaccharide (a1), and 2 to 2 carbon atoms. 4 can be produced by a method of obtaining compound (a12) from chemical reaction (1) with 20 to 80 parts by mole of alkylene oxide (a2).

  As the non-reducing di- or trisaccharide (a1), the same disaccharide or trisaccharide that can constitute the reaction residue (Q) in the general formula (1) can be used, and the preferred range is also the same.

  As alkylene oxide (a2), C2-C4 alkylene oxide etc. can be used, and ethylene oxide (eo), propylene oxide (po), butylene oxide (bo), these mixtures, etc. are mentioned. Among these, from the viewpoint of the surface tension reducing ability and water resistance obtained, eo, po, and eo and po are preferably mixed, and more preferably eo and po are mixed.

  In the case of using a plurality of types of alkylene oxide, the order of reaction (block shape, random shape and combinations thereof) and the use ratio are not limited, but it is preferable to include a block shape or a combination of block shape and random shape. When eo is used, the use ratio (mol%) of eo is preferably 1 to 30, more preferably 1 to 25, particularly preferably 3 to 25, and most preferably 3 based on the total number of moles of alkylene oxide. ~ 20. When eo and po or / and bo are included, it is preferable to react po and / or bo after the reaction of eo to the non-reducing di- or trisaccharide (a1).

  The amount (mole) of alkylene oxide (a2) used is preferably 10 to 80, more preferably 10 to 70, particularly preferably 20 to 70, most preferably per mole of non-reducing di- or trisaccharide (a1). Is 20-60. Within this range, the surface tension reducing ability is further improved.

  For the addition reaction between the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2), a known method (Japanese Patent Application Laid-Open No. 2004-224945) or the like can be applied, and anionic polymerization, cationic polymerization or coordination can be performed. You may implement in any forms, such as coordinate anionic polymerization. These polymerization forms may be used alone or in combination according to the degree of polymerization.

  For the addition reaction of alkylene oxide (a2), a known reaction catalyst (JP 2004-224945 A) can be used. In addition, when using the amide demonstrated below as a reaction solvent, it is not necessary to use a reaction catalyst.

  When the reaction catalyst is used, the amount used (% by weight) is preferably 0.01 to 1, based on the total weight of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). Preferably it is 0.03-0.8, Most preferably, it is 0.05-0.6. When it is within this range, the economy (required production time, catalyst cost, etc.), the purity of the product (monodispersity, etc.), etc. are further improved.

  When a reaction catalyst is used, it is preferable to finally remove the reaction catalyst from the reaction product. As the removal method, an alkali adsorbent such as synthetic aluminosilicate {for example, trade name: Kyoward 700, Kyowa Chemical Industry ( Co., Ltd., "Kyoward" is a registered trademark of the company. } (JP-A-53-123499, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (JP-B-49-14359, etc.), a method using an ion exchange resin (JP-A-51 No. 23211, etc.) and a method of filtering neutralized salts (hydrochloride, sulfate, carbonate, etc.) produced by neutralizing the reaction catalyst with an acid (mineral acid, carbon dioxide, etc.) (Japanese Patent Publication No. 52-33000) Publication etc.).

  The remaining amount of the reaction catalyst can be managed by the CPR (Controlled Polymerization Rate) value described in JIS K1557-4: 2007, the CPR value is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, Most preferably, it is 2 or less.

  A reaction solvent can be used in the step of the addition reaction of alkylene oxide (a2). As the reaction solvent, those having no active hydrogen are preferred, and more preferably those which dissolve the product produced by the reaction with the non-reducing disaccharide or trisaccharide (a1), alkylene oxide (a2) and (a2). Is preferred.

  As such a reaction solvent, alkyl amides having 3 to 8 carbon atoms and heterocyclic amides having 5 to 7 carbon atoms can be used.

  Examples of the alkylamide include N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-propylacetamide, 2-dimethylaminoacetaldehyde dimethylacetal and the like.

  Examples of the heterocyclic amide include N-methylpyrrolidone, N-methyl-ε-caprolactam, and N, N-dimethylpyrrolecarboxylic acid amide.

  Of these, alkylamide and N-methylpyrrolidone are preferred, DMF, N, N-dimethylacetamide and N-methylpyrrolidone are more preferred, DMF and N-methylpyrrolidone are most preferred, and DMF is most preferred.

  When a reaction solvent is used, the amount used (% by weight) is preferably 20 to 200, more preferably 40 to 180, based on the weight of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). Especially preferably, it is 60-150.

  When a reaction solvent is used, it is preferable to remove the reaction solvent after the reaction. The residual amount (% by weight) of the reaction solvent is preferably 0.1 or less, more preferably 0.05 based on the weight of the non-reducing di- or trisaccharide (a1) and alkylene oxide (a2). Hereinafter, it is particularly preferably 0.01 or less. The residual amount of the reaction solvent can be determined by gas chromatography using an internal standard substance.

  Examples of the method for removing the reaction solvent include the method described in JP-A-2005-132916.

  A known reaction vessel (JP 2004-224945 A) or the like can be used for the reaction. As the reaction atmosphere, it is preferable that the inside of the reaction apparatus is evacuated or dried in an inert gas (argon, nitrogen, carbon dioxide, etc.) atmosphere before introducing the alkylene oxide (a2) into the reaction system. Moreover, as reaction temperature (degreeC), 80-150 are preferable, More preferably, it is 90-130. The reaction pressure (gauge pressure: MPa, hereinafter the same) is preferably 0.8 or less, more preferably 0.5 or less.

  The end point of the reaction can be confirmed by the following method. That is, when the reaction temperature is kept constant for 15 minutes, the reaction end point is determined when the decrease in the reaction pressure becomes 0.001 MPa or less. The required reaction time is usually 4 to 12 hours.

  Prior to the start of reaction step (1), the water content (% by weight) is reduced to 2-5 based on the weight of alkali metal hydroxide (A), polyether compound (GP) and epihalohydrin (GE). It is preferable to adjust, more preferably 2.5 to 4.5, and particularly preferably 3 to 4. Within this range, the produced neutralized salt crystallizes greatly and can be easily removed by a desalting filtration step (for example, filter paper No. 2: manufactured by ADVANTEC, reserved particle diameter: 5 μm).

  In the reaction step (1), water is by-produced together with the neutralized salt. However, if the water content is within the above range at the start of the reaction, it may be exceeded in the middle of the reaction.

  When water is present in the reaction system, a side reaction described in JP-A-5-163260 occurs, and some glycidyl groups (epoxy groups) introduced into the polyether compound (GP) by ether bonds are exchanged with other polyesters. Although it is considered that the ring-opening reaction with the hydroxyl group of the ether compound (GP) results in partial multimerization, it can be used without any problem even if it is multimerized.

  The confirmation of the reaction end point in the reaction step (1) can be performed by the following method or the like. That is, when the pH of the reaction solution is measured and becomes 7 to 8, the reaction end point is reached. The required reaction time is usually 3 to 12 hours. In addition, pH can be measured by attaching a reaction liquid directly to a litmus paper and observing a color change (20-30 degreeC).

In the reaction step (1), the reaction conditions applied in the dehydrohalogenation reaction with a base (Willson synthesis method: the reaction is driven by neutralizing the hydrogen halide sequentially generated during the reaction with a base) are applied as they are. it can.
As the reaction vessel, it is preferable to use a reaction vessel capable of heating / cooling, stirring and dropping (press-fitting).
As reaction temperature (degreeC), about 30-90 are preferable, More preferably, it is 50-70.
As the reaction atmosphere, it is preferable to make the inside of the reaction apparatus an atmosphere of inert gas (argon, nitrogen, carbon dioxide, etc.) before introducing epihalohydrin into the reaction system.

  The preferable production method described above preferably includes a desalting filtration step (2) for removing the neutralized salt by-produced in the reaction step (1) by filtration after the reaction step (1), and more preferably After the reaction step (1), based on the weight of the glycidyl compound (G) obtained, the water content is 0.2 (preferably 0.1, more preferably 0.05) wt% or less. And a desalting filtration step (2) for removing the neutralized salt by-produced in the reaction step (1) by filtration.

A known method can be applied to the filtration, and normal natural filtration or vacuum filtration (suction filtration) may be used. Known filter media and filtration devices can be applied as they are.
As filtration temperature (degreeC), about 30-100 are preferable, More preferably, it is 50-90.

Subsequent to the reaction step (1), when the water content is 0.2% by weight or less based on the weight of the obtained glycidyl compound (G), the dehydration method is not limited, but the distillation under reduced pressure ( A method of dehydration under reduced pressure is preferred. Distillation under reduced pressure (dehydration under reduced pressure) can be removed together with water even if excess epihalohydrin (GE) remains.
When distilling off under reduced pressure, the pressure {gauge pressure (hereinafter the same)} is preferably about -0.05 to -0.098 MPa, and the temperature is preferably about 60 to 100 ° C.

  The water content (% by weight) can be measured by a known method, for example, by the Karl Fischer method (JIS K0113: 2005, coulometric titration method).

  When excess alkali metal hydroxide (A) remains at the end of the reaction step (1), it is preferably removed. As the removal method, the removal method of “reaction catalyst that can be used for addition reaction of alkylene oxide (a2)” described in the production method of the polyether compound (GP) can be applied. Among these, a method of filtering a neutralized salt (hydrochloride, sulfate, carbonate, etc.) produced by neutralizing an alkali metal hydroxide with an acid (mineral acid, carbon dioxide, etc.) is preferable. If the method of filtering is applied, since it can filter with the neutralized salt byproduced by reaction process (1), it is efficient. The residual amount may be further reduced by treating the alkali metal hydroxide (A) with an alkali adsorbent instead of or together with the filtration method.

  In addition, when neutralizing an alkali metal hydroxide with an acid, examples of acids include mineral acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), organic acids (formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, terephthalic acid, Oxalic acid, malonic acid, adipic acid, succinic acid, lactic acid, etc.) can be used.

  The remaining amount of the alkali metal hydroxide (A) can be managed by a CPR (Controlled Polymerization Rate) value described in JIS K1557-4: 2007. The CPR value is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less.

<Chemical reaction between active hydrogen-containing modified silicone (S) and glycidyl compound (G)>
The silicone modified body (Y) constituting the surfactant of the present invention is obtained by a chemical reaction between the active hydrogen-containing modified silicone (S) and the glycidyl compound (G) represented by the general formula (1). For this reaction (addition reaction), a known reaction catalyst (Japanese Patent Laid-Open No. 2004-224945 and the like) and / or a known reaction solvent (Japanese Patent Laid-Open No. 2003-160752 and the like) can be used. On the other hand, in this reaction, it can be produced without a reaction solvent and a reaction catalyst. In the latter case, a predetermined amount of the active hydrogen-containing modified silicone (S) and the glycidyl compound (G) are charged into a reaction vessel that can be heated, stirred, sealed, dehydrated, etc., dehydrated and heated up while stirring, 120 to 150 The reaction is completed at 2 ° C. for 2 to 8 hours.

  The end point of the reaction can be performed by the disappearance of the epoxy group. The epoxy group is quantified by cetyltrimethylammonium bromide (CTAB) method (JIS K7236) in which hydrogen halide (HB) is generated from perchloric acid and a quaternary ammonium salt (CTAB) and reacted with the epoxy group. : Conforming to ISO3001: 1999) is applicable.

  Dynamic surface (interface) tension reduction ability is the ability to reduce surface tension in a relatively short time after a new interface is formed by adding a surfactant or the like. It is the performance represented by the activator. The dynamic surface tension is a surface tension measured about a tenth of a second (also expressed as 100 milliseconds or 10 Hz) after a new interface is formed. When the dynamic surface tension reducing ability is low and a new interface is formed, the surface tension hardly decreases after about 1/10 second (dynamic surface tension reducing ability is low). As a method for measuring the dynamic surface tension, a bubble pressure method is generally used, and for example, it can be measured using a BP2 bubble pressure dynamic surface tension meter manufactured by Cruz.

  The dynamic surface tension {mN / m, 0.2 wt% aqueous solution, 25 ° C., surface life (foam life) 100 milliseconds (10 Hz)} of the surfactant of the present invention is 30 to 45, more preferably 30 to 43, particularly preferably 30 to 42, most preferably 30 to 40 is indicated.

  The static surface tension can be measured using, for example, an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. The surfactant of the present invention has a static surface tension {mN / m, 0.2 wt% aqueous solution, 25 ° C.} of 20 to 30, more preferably 20 to 28, particularly preferably 20 to 26, and most preferably. Indicates 20-25.

  In the above-mentioned Gemini type surfactant, although the dynamic surface tension reducing ability is generally excellent, the static surface tension reducing ability is inferior to ordinary surfactants. The surfactant of the present invention is excellent in both dynamic surface tension lowering ability and static surface tension lowering ability, and contains an aqueous coating agent composition {surfactant, water, resin binder and, if necessary, a colorant. It becomes. For example, it is suitable as a surfactant for water-based paints, paper coating paints, water-based inks, etc.} and is suitable as a surfactant for aqueous coating agent compositions for high-speed coating. Curtain flow coat, etc.), high-speed coating paper coating liquid, water-based ink for high-speed printing, or jet type ink and the like.

  When the surfactant of the present invention is applied to an aqueous coating composition, film defects such as repelling can be effectively suppressed. In addition, since the conformity to the coated surface, wettability, etc. during the high-speed coating of the aqueous coating agent composition can be drastically improved, excellent coating suitability (improvement of film breakage, smoothness, etc.) is exhibited.

  When the surfactant of the present invention is applied to an aqueous coating agent composition, the surfactant of the present invention is a pigment dispersion step, a letdown step and / or various regulators (among the production steps of the aqueous coating agent composition). Viscosity modifiers, antioxidants, wetting agents, UV absorbers, antifoaming agents, dispersants, water retention agents, fluidity modifiers, etc.) may be added, etc. It may also be added to the aqueous coating agent composition after production.

  When the surfactant of the present invention is applied to an aqueous coating agent composition, the addition amount (% by weight) of the surfactant of the present invention is preferably 0.1 to 5, based on the weight of the aqueous coating agent. Preferably it is 0.1-4, Most preferably, it is 0.2-3.5, Most preferably, it is 0.5-3.

  The aqueous coating agent composition containing the surfactant of the present invention can be applied or printed on a substrate by an ordinary method, and is applied by brush coating, roller coating, air spray coating, airless coating, roll coat coating, curtain. Coating methods or printing methods such as flow coat coating, gravure printing, and ink jet printing can be applied. Of these, curtain flow coat coating, gravure printing, and ink jet printing are preferred from the viewpoint that high-speed coating properties can be exhibited.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

<Production Example 1>
In a pressure-resistant reaction vessel capable of heating, stirring, cooling, dropping, pressurizing with nitrogen, and depressurization with a vacuum pump, 342 parts (1 mol part) of purified granulated sugar {manufactured by Taiyo Co., Ltd.) and N, N-dimethylformamide ( Hereinafter, abbreviated as DMF.) After charging 800 parts, the operation of pressurizing with nitrogen gas to 0.4 MPa and then discharging to 0.02 MPa was repeated three times (hereinafter referred to as “DMF”). Abbreviated as nitrogen substitution). Furthermore, after heating up to 100 degreeC, stirring, 290 parts (5 mol parts) of propylene oxide (po) was dripped at this temperature over 4 hours. Subsequently, 360 parts (5 parts by mole) of butylene oxide (bo) was added dropwise at this temperature over 4 hours, followed by stirring at the same temperature for 3 hours to react the remaining butylene oxide (bo). Next, DMF was distilled off under reduced pressure (−0.05 to −0.098 MPa: hereinafter simply referred to as “reduced pressure”) to obtain a polyether compound (GP1) {sucrose / (po) 5 mol / (bo). 5 mol adduct} was obtained.

  In a pressure-resistant reaction vessel similar to the above, 992 parts (1 mole part) of a polyether compound (GP1) and sodium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., purity of about 97% by weight, the amount used is water. It is displayed as the net equivalent converted amount. The same applies hereinafter. } 40 parts (1 mole part) and 35 parts of water were charged, and the mixture was stirred at 60 ° C., and epichlorohydrin (GE1) {manufactured by Daiso Co., Ltd., hereinafter the same. } 111 parts (1.2 mole parts) was added dropwise over 3 hours. Subsequently, stirring is continued at 60 ° C. for 5 hours, and the pH of the reaction solution is 7 {by litmus test paper (manufactured by TOYO ROSHI CO. LTD, product name: UNIV PH 1-11). same as below. } Was confirmed. Subsequently, the remaining epichlorohydrin was distilled off and dehydrated at 80 ° C. under reduced pressure (water content: 0.03% or less, hereinafter simply referred to as dehydration under reduced pressure). 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd., reserved particle diameter: 5 μm, and so on. } To obtain a glycidyl compound (G1) {sucrose / (po) 5 mol / (bo) 5 mol / (GE1) 1 mol adduct)}.

<Production Example 2>
Into a pressure resistant reactor similar to Production Example 1, 342 parts (1 mol part) of purified granulated sugar and 800 parts of DMF were added, and then nitrogen substitution was performed. Further, the mixture was heated to 100 ° C. while stirring, and then 870 parts (15 mole parts) of propylene oxide (po) was added dropwise at this temperature over 7 hours, followed by stirring at the same temperature for 3 hours. Subsequently, the remaining propylene oxide (po) was reacted. Next, DMF was distilled off under reduced pressure to obtain a polyether compound (GP2) {sucrose / (po) 15 mol adduct}.

  Next, in a pressure-resistant reaction vessel similar to Production Example 1, 1212 parts (1 mole part) of a polyether compound (GP2) and 3 parts of potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. It is displayed as the net equivalent converted amount. The same applies hereinafter. } And dehydrated under reduced pressure at 120 ° C. for 1 hour. Next, 360 parts (5 parts by mole) of butylene oxide (bo) was added dropwise at 100 ° C. over 3 hours with the same reduced pressure, and the remaining butylene oxide (bo) was allowed to react by continuing stirring at this temperature for 2 hours. As a result, a crude reaction liquid was obtained. After adding 30 parts of ion-exchanged water to the crude reaction liquid and raising the temperature to 90 ° C. with stirring, 50 parts of Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) is added and this temperature is maintained for 1 hour. Then, the Kyodo 700 is removed using a filter paper, and further dehydrated at 120 ° C. for 1 hour under reduced pressure {hereinafter simply referred to as Kyoward treatment. } To obtain a polyether compound (GP3) {sucrose / (po) 15 mol / (bo) 5 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1572 parts (1 mole part) of a polyether compound (GP3), 40 parts (1 mole part) of sodium hydroxide and 70 parts of water, and these were stirred at 60 ° C. Then, 111 parts (1.2 mol parts) of epichlorohydrin (GE1) was added dropwise over 3 hours. Subsequently, stirring was continued for 5 hours at 60 ° C., and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration with filter paper was performed to obtain a glycidyl compound (G2) {sucrose / (po) 15 mol / (bo) 5 mol / (GE1) 1 mol adduct}.

<Production Example 3>
A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1212 parts (1 mol part) of a polyether compound (GP2) {sucrose / (po) 15 mol adduct} and 4 parts of potassium hydroxide at 120 ° C. under reduced pressure. Dehydrated for 1 hour. Next, 870 parts (15 mole parts) of propylene oxide (po) was added dropwise at 100 ° C. over 4 hours with the same reduced pressure, and the remaining propylene oxide (po) was reacted by continuing stirring at this temperature for 2 hours. As a result, a crude reaction liquid was obtained. 35 parts of ion-exchanged water was added to the crude reaction liquid, and the temperature was raised to 90 ° C. while stirring. Then, 60 parts of Kyoward 700 was added and stirred at this temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyether compound (GP4) {sucrose / (po) 30 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 2082 parts (1 mole part) of a polyether compound (GP4), 48 parts (1.2 mole parts) of sodium oxide and 70 parts of water, and these were stirred at 60 ° C. Then, 139 parts (1.5 mole parts) of epichlorohydrin (GE1) was added dropwise over 4 hours. Subsequently, stirring was continued at this temperature for 5 hours, and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration with filter paper is performed, and glycidyl compound (G3) {80 mol% of sucrose / (po) 30 mol / (GE1) 1 mol adduct and sucrose / (po) 30 A mixture with 20 mol% of mol / (GE1) 2 mol adduct; P ″ = 1.2} was obtained.

<Production Example 4>
A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1212 parts (1 mol part) of a polyether compound (GP2) {sucrose / (po) 15 mol adduct} and 5 parts of potassium hydroxide at 120 ° C. under reduced pressure. Dehydrated for 1 hour. Next, 1450 parts (25 mole parts) of propylene oxide (po) was added dropwise at 100 ° C. over 5 hours with the same reduced pressure, and the remaining propylene oxide (PO) was reacted by continuing stirring at this temperature for 3 hours. As a result, a crude reaction liquid was obtained. 45 parts of ion-exchanged water was added to the crude reaction liquid, and the temperature was raised to 90 ° C. while stirring. 65 parts of Kyoward 700 was added and stirred at this temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyether compound (GP5) {sucrose / (PO) 40 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 2662 parts (1 mole part) of a polyether compound (GP5), 60 parts (1.5 mole parts) of sodium hydroxide and 110 parts of water at 60 ° C. While stirring, 167 parts (1.8 mol parts) of epichlorohydrin (GE1) was added dropwise over 4 hours. Subsequently, stirring was continued for 5 hours at 60 ° C., and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration with filter paper is performed, and glycidyl compound (G4) {sucrose / (po) 40 mol / (GE1) 1 mol adduct 50 mol% and sucrose / (po) 40 A mixture with 50 mol% of mol / (GE1) 2 mol adduct; P ″ = 1.5} was obtained.

<Production Example 5>
A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1212 parts (1 mol part) of a polyether compound (GP2) {sucrose / (po) 15 mol adduct} and 7 parts of potassium hydroxide at 120 ° C. under reduced pressure. Dehydrated for 1 hour. Next, 2610 parts (45 mole parts) of propylene oxide (po) was added dropwise at 100 ° C. over 7 hours while maintaining the same reduced pressure, and the remaining propylene oxide (po) was reacted by continuing stirring at this temperature for 3 hours. As a result, a crude reaction liquid was obtained. After adding 80 parts of ion-exchanged water to the crude reaction liquid and raising the temperature to 90 ° C. with stirring, 100 parts of Kyoward 700 was added and stirred at this temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyether compound (GP6) {sucrose / (po) 60 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 3822 parts (1 mole part) of a polyether compound (GP6), 80 parts (2 mole parts) of sodium hydroxide and 140 parts of water, and these were stirred at 60 ° C. Then, 213 parts (2.3 mol parts) of epichlorohydrin (GE1) was added dropwise over 5 hours. Subsequently, stirring was continued for 5 hours at 60 ° C., and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration using filter paper was performed to obtain a glycidyl compound (G5) {sucrose / (po) 60 mol / (GE1) 2 mol adduct}.

<Production Example 6>
Into a pressure resistant reactor similar to Production Example 1, 342 parts (1 mol part) of purified granulated sugar and 800 parts of DMF were added, and then nitrogen substitution was performed. Further, the temperature of the mixture was increased to 100 ° C. with stirring, and then 440 parts (15 mole parts) of ethylene oxide (eo) was added dropwise at this temperature over 3 hours, and then 580 parts (10 parts of propylene oxide (po)). Mol part) was added dropwise over 6 hours, followed by stirring at the same temperature for 3 hours to react with the remaining propylene oxide (PO). Next, DMF was distilled off under reduced pressure to obtain a polyether compound (GP7) {sucrose / (eo) 10 mol / (po) 10 mol adduct).

  Subsequently, 1362 parts (1 mol part) of a polyether compound (GP7) and 9 parts of potassium hydroxide were charged into the same pressure resistant reaction vessel as in Production Example 1, and dehydrated at 120 ° C. for 1 hour under reduced pressure. Next, 2100 parts (50 mole parts) of propylene oxide (po) was added dropwise at 100 ° C. over 8 hours with the same reduced pressure, and the remaining propylene oxide (po) was reacted by continuing stirring at this temperature for 3 hours. As a result, a crude reaction liquid was obtained. Next, Kyoward treatment was performed to obtain a polyether compound (GP8) {sucrose / (eo) 10 mol / (po) 60 mol adduct}.

  In a pressure-resistant reaction vessel similar to Production Example 1, 4262 parts (1 mole part) of a polyether compound (GP8), 72 parts (1.8 mole parts) of sodium hydroxide and 180 parts of water were charged at 60 ° C. While stirring, 185 parts (2 mole parts) of epichlorohydrin (GE1) was added dropwise over 4 hours. Subsequently, stirring was continued for 5 hours at 60 ° C., and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration with a filter paper was performed, and glycidyl compound (G6) {sucrose / (eo) 10 mol / (po) 60 mol / (GE1) 1 mol adduct 20 mol%, A mixture of sucrose / (eo) 10 mol / (po) 60 mol / (GE1) 2 mol adduct 80 mol%; P ″ = 1.8} was obtained.

<Production Example 7>
The same pressure-resistant reaction vessel as in Production Example 1 is trehalose {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., and so on. } After charging 504 parts (1 mole part) and 1000 parts of DMF, nitrogen substitution was performed. The mixture was heated to 100 ° C. while stirring, and then 870 parts (15 mole parts) of propylene oxide (po) was added dropwise over 6 hours at this temperature, and the stirring was continued at this temperature for 3 hours. The remaining propylene oxide (po) was reacted. Next, DMF was distilled off under reduced pressure to obtain a polyether compound (GP9) {trehalose / (po) 15 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1374 parts (1 mole part) of a polyether compound (GP9) and 3 parts of potassium hydroxide, and dehydrated at 120 ° C. for 1 hour under reduced pressure. Next, 360 parts (5 parts by mole) of butylene oxide (bo) was added dropwise at 100 ° C. over 3 hours with the same reduced pressure, and the remaining butylene oxide (bo) was allowed to react by continuing stirring at this temperature for 2 hours. As a result, a crude reaction liquid was obtained. Next, it was treated with Kyoward to obtain a polyether compound (GP10) {trehalose / (po) 15 mol / (bo) 5 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1734 parts (1 mole part) of a polyether compound (GP10), 60 parts (1.5 mole parts) of sodium hydroxide and 80 parts of water. 167 parts (1.8 mole parts) of epichlorohydrin (GE1) was added dropwise over 5 hours while stirring at -5. Subsequently, stirring was continued for 5 hours at 60 ° C., and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration with a filter paper was performed, and glycidyl compound (G7) {trehalose / (po) 15 mol / (bo) 5 mol / (GE1) 1 mol adduct 50 mol%, A mixture of trehalose / (po) 15 mol / (bo) 5 mol / (GE1) 2 mol adduct 50 mol%; P ″ = 1.5} was obtained.

<Production Example 8>
A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1374 parts (1 mol part) of a polyether compound (GP9) {trehalose / (po) 15 mol adduct} and 6 parts of potassium hydroxide at 120 ° C. under reduced pressure. Dehydrated for 1 hour. Subsequently, 1450 parts (25 mole parts) of propylene oxide (po) was added dropwise over 5 hours at 100 ° C. with the same reduced pressure, and the remaining propylene oxide (po) was reacted by continuing stirring at this temperature for 3 hours. As a result, a crude reaction liquid was obtained. Next, it was subjected to Kyoward treatment to obtain a polyether compound (GP11) {trehalose / (po) 40 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 2824 parts (1 mole part) of a polyether compound (GP11), 60 parts (1.5 mole parts) of sodium hydroxide and 100 parts of water. While stirring at ° C., 167 parts (1.8 mol parts) of epichlorohydrin (GE1) was added dropwise over 5 hours. Subsequently, stirring was continued for 5 hours at 60 ° C., and it was confirmed that the pH of the reaction solution became 7. Subsequently, after dehydrating under reduced pressure at 80 ° C., suction filtration with filter paper is performed, and glycidyl compound (G8) {trehalose / (po) 40 mol / (GE) 1 mol adduct 50 mol% and trehalose / (po) 40 A mixture with 50 mol% of mol / (GE) 2 mol adduct; P ″ = 1.5} was obtained.

<Production Example 9>
Into a pressure resistant reactor similar to Production Example 1, 504 parts (1 mole part) of Meletitose {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1000 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the mixture was heated to 110 ° C. with stirring, and at this temperature, 440 parts (10 mole parts) of ethylene oxide (eo) and 290 parts (5 mole parts) of propylene oxide (po) were mixed. The mixture was added dropwise over a period of time, and stirring was continued at this temperature for 2 hours to react the remaining ethylene oxide (eo) and propylene oxide (po). Next, DMF was distilled off under reduced pressure to obtain a polyether compound (GP12) {meletitol / (eo) 10 mol · (po) 5 mol random adduct).

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 1234 parts (1 mole part) of a polyether compound (GP12) and 9 parts of potassium hydroxide, and dehydrated at 120 ° C. for 1 hour under reduced pressure. Next, 2610 parts (45 mole parts) of propylene oxide (po) was added dropwise at 100 ° C. over 7 hours while maintaining the same reduced pressure, and the remaining propylene oxide (po) was reacted by continuing stirring at this temperature for 3 hours. As a result, a crude reaction liquid was obtained. Next, Kyoward treatment was performed to obtain a polyether compound (GP13) {meletitol / (eo) 10 mol · (po) 5 mol / (po) 45 mol adduct)}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 3844 parts (1 mole part) of a polyether compound (GP12), 80 parts (2 mole parts) of sodium hydroxide and 130 parts of water, and the mixture at 60 ° C. While stirring, 213 parts (2.3 mol parts) of epichlorohydrin (GE1) was added dropwise over 5 hours. Subsequently, stirring was continued at 60 ° C. for 6 hours, and it was confirmed that the pH of the reaction solution became 7. Then, after dehydrating under reduced pressure at 80 ° C., suction filtration with filter paper is performed, and glycidyl compound (G9) {meletitol / (eo) 10 mol · (po) 5 mol / (po) 45 mol / (GE1) 2 mol addition Thing} was obtained.

<Production Example 10>
1234 parts (1 mole part) of a polyether compound (GP12) and 10 parts of potassium hydroxide were charged and dehydrated at 120 ° C. under reduced pressure for 1 hour. Next, 3770 parts (65 mole parts) of propylene oxide (po) was added dropwise over 10 hours at 100 ° C. with the same reduced pressure, and the remaining propylene oxide (po) was reacted by continuing stirring at this temperature for 3 hours. As a result, a crude reaction liquid was obtained. Next, Kyoward treatment was carried out to obtain a polyether compound (GP14) {meletitol / (eo) 10 mol · (po) 5 mol / (po) 65 mol adduct}.

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 5004 parts (1 mole part) of a polyether compound (GP14), 120 parts (3.0 mole parts) of sodium hydroxide and 150 parts of water. While stirring at ° C., 305 parts (3.3 mol parts) of epichlorohydrin (GE1) was added dropwise over 5 hours. Subsequently, stirring was continued at 60 ° C. for 6 hours, and it was confirmed that the pH of the reaction solution became 7. Next, after dehydrating under reduced pressure at 80 ° C., suction filtration with filter paper is performed, and glycidyl compound (G10) {meletitol / (eo) 10 mol · (po) 5 mol / (po) 65 mol / (GE1) 3 mol addition Thing} was obtained.

<Production Example 11>
(1) Production of hydrogen polysiloxane (HP1) Octamethylcyclotetrasiloxane {reagent special grade, manufactured by Tokyo Chemical Industry Co., Ltd.} in a reaction vessel that can be heated, stirred, cooled, dripped, depressurized by a condenser and a vacuum pump 1628 parts (5.5 mole parts), tetramethyltetrahydrocyclotetrasiloxane {reagent special grade, manufactured by Tokyo Chemical Industry Co., Ltd.} 360 parts (1.5 mole parts), hexamethyldisiloxane {reagent special grade, Tokyo Chemical Industry Co., Ltd. 210 parts (1.3 parts by mole) manufactured by Co., Ltd. and 1 part (0.025 parts by mole) of sodium hydroxide were added and stirring was continued at 90 ° C. for 6 hours.

Next, the mixture was cooled to 25 ° C., 1.5 parts (0.025 mol part) of formic acid was added, stirred for 0.5 hour, and then heated at a rate of 20 ° C./1 hour while reducing the pressure. Stripping was further performed at −0.095 MPa for 2 hours to obtain hydrogen polysiloxane (HP1). ¹ H-NMR analysis and IR analysis confirmed that the hydrogen polysiloxane (HP1) had the following structure {Me represents a methyl group, Si represents a silicon atom, O represents an oxygen atom, and H represents a hydrogen atom. }.

(2) Production of allyl alcohol / (eo) 15 mol / (po) 2 mol adduct (AA1) In a pressure-resistant reaction vessel similar to Production Example 1, allyl alcohol {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} After charging 59 parts (1 mole part) and 1.1 parts of potassium hydroxide, pressurization with nitrogen at a liquid temperature of 20 ° C. until reaching 0.4 MPa (gauge pressure), 0.02 MPa (gauge pressure) The discharge of nitrogen to the extent was repeated three times. Subsequently, 660 parts (15 mol parts) of ethylene oxide (eo) was added dropwise over 3 hours while stirring at 100 ° C. Next, 116 parts (2 mole parts) of propylene oxide (po) was added dropwise over 2 hours, followed by further reaction at 120 ° C. for 2 hours. Next, Kyoward treatment was performed to obtain an allyl alcohol / (eo) 15 mol / (po) 2 mol adduct (AA1).

(3) Production of hydroxyl group-containing polyether-modified silicone (S101) Hydrogenpolysiloxane (HP1) 1186 obtained in (1) above was placed in a reaction vessel capable of heating, stirring, cooling, dropping, depressurization with a condenser and a vacuum pump. Part (1 mole part), allyl alcohol obtained in (2) above / (eo) 15 mole / (po) 2 mole adduct (AA1) 1670 parts (2 mole parts), isopropyl alcohol 2000 parts and chloroplatinic acid 2 parts of an isopropyl alcohol solution (content of chloroplatinic acid: 5 × 10 ⁻⁶ %) was added, and stirring was continued for 7 hours under reflux. Next, the solvent was removed at 90 to 100 ° C. under reduced pressure to obtain a hydroxyl group-containing polyether-modified silicone (S101).

<Example 1>
In a pressure resistant reactor similar to Production Example 1, 100 parts of the hydroxyl group-containing polyether-modified silicone (S101) obtained in Production Example 11 (containing 0.07 mol part of active hydrogen) and the glycidyl compound obtained in Production Example 1 (G1) ) 20 parts (0.019 mol part) were added and dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y1) of the present invention was obtained.

<Example 2>
In a pressure resistant reactor similar to Production Example 1, 100 parts of hydroxyl group-containing modified silicone (S101) (containing 0.07 mol part of active hydrogen) and 150 parts of glycidyl compound (G5) obtained in Production Example 5 (0.038 mol) Part) was dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y2) of the present invention was obtained.

<Example 3>
In a pressure resistant reactor similar to Production Example 1, 100 parts of hydroxyl group-containing modified silicone (S101) (containing 0.07 mol part of active hydrogen) and 50 parts of glycidyl compound (G2) obtained in Production Example 2 (0.031 mol) Part) was dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y3) of the present invention was obtained.

<Example 4>
In a pressure-resistant reaction vessel similar to Production Example 1, 100 parts of hydroxyl group-containing polyether-modified silicone (S102) {SN Wet 125, manufactured by San Nopco Co., Ltd.} and 100 parts of the glycidyl compound (G3) obtained in Production Example 3 were charged. Dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y4) of the present invention was obtained.

<Example 5>
In a pressure-resistant reaction vessel similar to Production Example 1, 100 parts of a hydroxyl group-containing polyether-modified silicone (S102) and 10 parts of the glycidyl compound (G1) obtained in Production Example 1 were charged and dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y5) of the present invention was obtained.

<Example 6>
In a pressure resistant reaction vessel similar to Production Example 1, 100 parts of a hydroxyl group-containing polyether-modified silicone (S102) and 40 parts of the glycidyl compound (G4) obtained in Production Example 4 were charged and dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group, and the surfactant (Y6) of the present invention was obtained.

<Example 7>
Hydroxyl-containing polyether-modified silicone (S103) {SH3771, molecular weight per mole of active hydrogen (hydroxyl equivalent = active hydrogen equivalent) 800, manufactured by Toray Dow Corning Co., Ltd.} 100 parts (containing active hydrogen 0.125 moles) Then, 100 parts (0.034 mol part) of the glycidyl compound (G8) obtained in Production Example 8 was charged and dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 7 hours to confirm the disappearance of the epoxy group, and the surfactant (Y7) of the present invention was obtained.

<Example 8>
100 parts of hydroxyl group-containing polyether-modified silicone (S103) (containing 0.125 mole part of active hydrogen) and 80 parts (0.044 mole part) of the glycidyl compound (G7) obtained in Production Example 7 were charged at 120 ° C. Dehydrated under reduced pressure for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y8) of the present invention was obtained.

<Example 9>
Hydroxyl-containing polyether-modified silicone (S104) {X-22-6266, molecular weight per mole of active hydrogen (hydroxyl equivalent = active hydrogen equivalent) 1200, manufactured by Shin-Etsu Chemical Co., Ltd.} 100 parts (containing 0.083 moles) Then, 30 parts (0.01 mol part) of the glycidyl compound (G8) obtained in Production Example 8 was charged and dehydrated under reduced pressure at 120 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 5 hours to confirm the disappearance of the epoxy group, and the surfactant (Y9) of the present invention was obtained.

<Example 10>
100 parts of hydroxyl group-containing polyether-modified silicone (S104) (containing 0.083 mole part of active hydrogen) and 40 parts (0.019 mole part) of the glycidyl compound (G3) obtained in Production Example 3 were charged at 120 ° C. Dehydrated under reduced pressure for 1 hour. Subsequently, stirring was continued at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group, and the surfactant (Y10) of the present invention was obtained.

<Example 11>
Amino group-containing amino-modified silicone (S201) {KF-864, molecular weight per mole of active hydrogen (active hydrogen equivalent) 3800, manufactured by Shin-Etsu Chemical Co., Ltd.} 100 parts (containing active hydrogen 0.026 mole parts) and production examples 200 parts (0.039 mole part) of the glycidyl compound (G10) obtained in Step 10 was charged and dehydrated under reduced pressure at 80 ° C. for 1 hour. Subsequently, stirring was continued at 100 ° C. for 2 hours to confirm the disappearance of the epoxy group, and the surfactant (Y11) of the present invention was obtained.

<Example 12>
Carboxy group-containing carboxy-modified silicone (S301) {X-22-3701E, molecular weight per mol of active hydrogen (carboxy equivalent = active hydrogen equivalent) 4000, manufactured by Shin-Etsu Chemical Co., Ltd.} 100 parts (containing 0.025 mol of active hydrogen) ) And 150 parts (0.034 mol part) of the glycidyl compound (G6) obtained in Production Example 6 were added and dehydrated under reduced pressure at 100 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group, and the surfactant (Y12) of the present invention was obtained.

<Example 13>
Hydroxyl-containing carbinol-modified silicone (S401) {SF8428, molecular weight per mole of active hydrogen (hydroxyl equivalent = active hydrogen equivalent) 1600, manufactured by Toray Dow Corning Co., Ltd.} 100 parts (containing active hydrogen 0.063 moles) 180 parts (0.046 mol part) of the glycidyl compound (G9) obtained in Production Example 9 was charged and dehydrated under reduced pressure at 100 ° C. for 1 hour. Subsequently, stirring was continued at 130 ° C. for 6 hours to confirm the disappearance of the epoxy group, and the surfactant (Y13) of the present invention was obtained.

<Example 14>
Phenolic hydroxyl group-containing phenol-modified silicone (S501) {BY16-150S, molecular weight per mole of active hydrogen (hydroxyl equivalent = active hydrogen equivalent) 1550, manufactured by Toray Dow Corning Co., Ltd.} 100 parts (active hydrogen 0.065 moles) Content) and 200 parts (0.051 mol) of the glycidyl compound (G9) obtained in Production Example 9 were charged and dehydrated under reduced pressure at 100 ° C. for 1 hour. Subsequently, stirring was continued at 120 ° C. for 6 hours to confirm the disappearance of the epoxy group, and the surfactant (Y14) of the present invention was obtained.

<Example 15>
Mercapto group-containing mercapto-modified silicone (S601) {KF-2001, molecular weight per mole of active hydrogen (mercapto equivalent = active hydrogen equivalent) 1900, manufactured by Shin-Etsu Chemical Co., Ltd.} 100 parts (containing active hydrogen 0.053 mole part) And 150 parts (0.029 mol part) of the glycidyl compound (G10) obtained in Production Example 10 were charged and dehydrated under reduced pressure at 80 ° C. for 1 hour. Subsequently, stirring was continued at 100 ° C. for 4 hours to confirm the disappearance of the epoxy group, and the surfactant (Y15) of the present invention was obtained.

<Comparative Example 1>
100 parts of the hydroxyl group-containing polytel-modified silicone (S101) obtained in Production Example 11 and 100 parts of Surfynol 465 {Shin-Etsu Chemical Co., Ltd., acetylene glycol ethoxylate} are uniformly mixed to obtain a comparative surface activity. An agent (HY1) was obtained.

<Comparative example 2>
A comparative surfactant (HY2) was obtained by uniformly mixing 100 parts of a hydroxyl group-containing polytel-modified silicone (S101) and 50 parts of the glycidyl compound (G2) obtained in Production Example 4.

<Comparative Example 3>
Hydroxyl group-containing polytel-modified silicone (S101) was used as a comparative surfactant (HY3).

  The surfactants (Y1) to (Y15) of the present invention obtained in Examples 1 to 15 and the surfactants (H1Y) to (HY3) for comparison obtained in Comparative Examples 1 to 3 are as follows. The performance was evaluated.

1. Evaluation of surface tension Dynamic surface tension and static surface tension were measured by the following methods.

<Dynamic surface tension>
The evaluation samples {surfactants (Y1) to (Y15) of the present invention and comparative surfactants (HY1) to (HY3)} obtained in Comparative Examples 1 to 3) were dissolved in deionized water to obtain 0.2. % Aqueous solution at 25 ± 0.2 ° C. (liquid temperature, room temperature) using a bubble pressure type dynamic surface tension meter Cruz BP-2 manufactured by Cruz Co., Ltd., with a surface life of 50 Hz (20 milliseconds) to The surface tension at 0.1 Hz (10 seconds) was measured, and the dynamic surface tension at 10 Hz (100 milliseconds) is shown in Table 2.
The results of measuring the dynamic surface tension of the surfactant (Y3) obtained in Example 3 and the comparative surfactants (HY1) to (HY3) obtained in Comparative Examples 1 to 3 are shown in FIG. (The horizontal axis is the surface life (milliseconds) and the vertical axis is the surface tension (mN / m)}.

<Static surface tension>
An evaluation sample is dissolved in deionized water to prepare a 0.2% aqueous solution. At 25 ± 0.2 ° C. (liquid temperature, room temperature), an automatic surface tension meter CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd. Was used to measure the surface tension.

2. Evaluation of film resistance and smoothness of coating liquid curtain Prepare a curtain coating liquid containing an evaluation sample as follows, and evaluate the film resistance and smoothness of the coating liquid curtain. The results are shown in Table 4.

(1) Preparation of curtain coating solution The composition shown in Table 3 was prepared using an Excel auto homogenizer equipped with impeller blades (Model ED manufactured by Nippon Seiki Co., Ltd.).

Note 1: Heavy calcium carbonate, manufactured by Imeris Minerals Japan Co., Ltd. Note 2: Grade 1 kaolin, Engelhard Co., Ltd. Note 3: Grade 2 kaolin, Shiraishi Kogyo Co., Ltd. Note 4: Light calcium carbonate, Shiraishi Kogyo Co., Ltd. Note 5: Dispersant, San Nopco Co., Ltd. Note 6: Thickener, San Nopco Co., Ltd. Note 7: SBR Latex, JSR Co., Ltd. Note 8: Deionized water Note 9: Surfactant; Evaluation sample {Surfactants for use (Y1) to (Y15) and (HY1) to (HY3)}} Deionized water was used in the blank.

  The created curtain coating solution was measured for the degree of dispersion according to JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983), and it was confirmed that there were no particles of 5 microns or more.

(2) Resistance to film breakage of coating liquid curtain Curing coating liquid was applied at a curtain flow coater (Flow coater FL-W6G, manufactured by Anest Iwata Co., Ltd.) at a coating speed of 200 m / min, coating amount (basis weight when dried) ) Under a condition of 15 g / m ² , the number of film breaks (number of occurrences per minute) that occurred when coating on high-quality winding roll paper with a basis weight of 64 g / m ² and curtain coating was performed. The number of cuts is shown in Table 4. It can be said that the smaller the numerical value, the better the resistance to film breakage (coating property).

(3) Smoothness The high-quality roll-up roll paper coated with the curtain coating liquid is calendered (Auto Dryer L-3D, manufactured by Japoe, 130 ° C., 1 minute, treatment pressure 0.3 kg / cm ² ), Curtain coated paper was obtained. The smoothness of the curtain-coated paper was measured at 25 ± 0.2 ° C. and 50 ± 5% relative humidity using a smoother smoothness tester (manufactured by Toei Denshi Kogyo Co., Ltd., model SM-6A). The smoothness was measured and shown in Table 4. It can be said that the smaller the number, the better the smoothness.

3. Evaluation of ink repellency (1) Preparation of evaluation ink 100 parts of Super Ecoviewer {water-based gravure ink, for plastic film, manufactured by Sakata Inks Co., Ltd.}, an evaluation sample {surfactants (Y1) to (Y15) And 1 part of (HY1) to (HY3)} (1 part of deionized water was added to the blank), and the mixture was stirred with an Excel auto homogenizer equipped with impeller blades at 2000 rpm for 2 minutes, and then the defoamer { An evaluation ink was prepared by defoaming for 1 minute using model AR-250} manufactured by Awatori Nertaro Co., Ltd.

(2) Evaluation of repellency resistance An applicator on a polyester film (length: 150 mm, width: 150 mm, thickness: 0.10 mm, Toray Mirror L-100T60, manufactured by Toray Industries, Inc.) obtained by degreasing the evaluation ink with acetone. Was applied at a wet film thickness of 0.076 mm (7 cm × 10 cm), and the number of cissing marks immediately after coating was counted, and this number was defined as repellency resistance. These results are shown in Table 5.

 The surfactant of the present invention exhibits superior surface tension lowering ability (dynamic surface tension lowering ability, static surface tension lowering ability), and the number of film breaks and smoothness compared to a comparative surfactant. Both were good and also excellent in repelling resistance.

  The surfactant of the present invention can be used for any application, but is particularly suitable for an aqueous coating solution, and further suitable for paints, inks and the like that are applied or printed at high speed.

Claims (7)

A surfactant comprising a modified silicone (Y) obtained by chemically reacting an active hydrogen-containing modified silicone (S) with a glycidyl compound (G) represented by the general formula (1).

_{{E (-OA) n} p} -Q - {(AO-) n H} t-p (1)

In general formula (1), E is a glycidyl (1,2-epoxypropyl) group, H is a hydrogen atom, Q is a reaction residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide. Group, OA and AO are oxyalkylene groups having 2 to 4 carbon atoms, n is an integer of 1 to 40, t is an integer of 2 to 4, p is an integer of 1 to 3 (provided that t ≧ p), The total number of oxyalkylene groups (OA and AO) in the glycidyl compound (G) represented by the formula (1) is an integer of 10 to 80. Active hydrogen-containing modified silicone (S) is a hydroxyl group-containing polyether-modified silicone (S1), an amino group-containing amino-modified silicone (S2), a carboxy group-containing carboxy-modified silicone (S3), a hydroxyl group-containing carbinol-modified silicone (S4), The surfactant according to claim 1, which is at least one selected from the group consisting of a phenolic hydroxyl group-containing phenol-modified silicone (S5) and a mercapto group-containing mercapto-modified silicone (S6). The surfactant according to claim 1, wherein the active hydrogen-containing modified silicone (S) is a hydroxyl group-containing polyether-modified silicone (S1). The surfactant according to any one of claims 1 to 3, wherein Q is a reaction residue obtained by removing a hydrogen atom from three primary hydroxyl groups of sucrose. The interface according to any one of claims 1 to 4, wherein the amount of the glycidyl compound (G) represented by the general formula (1) is 10 to 200% by weight based on the weight of the active hydrogen-containing modified silicone (S). Activator. A method for producing the surfactant according to claim 1,
Including the step of chemically reacting the active hydrogen-containing modified silicone (S) and the glycidyl compound (G) represented by the general formula (1) to obtain a silicone-modified product (Y) without a reaction solvent and a reaction catalyst. A method for producing a surfactant, characterized in that It consists of an aqueous coating agent and the surfactant described in any one of claims 1 to 6, wherein the surfactant is contained in an amount of 0.1 to 5% by weight based on the weight of the aqueous coating agent. A water-based coating agent composition.

Images