Polyalkoxyalkylene compound and surface tension regulator

Abstract

To provide a surface tension regulator such as a surface modifier for electronic components, which is highly hydrophilic at the time of coating on a surface of a coating target, and allows the surface to be hydrophobized after undergoing post-coating thermal processing or other manufacturing processes.SOLUTION: A polyoxyalkylene compound is represented by the following formula (1). The compound has a number average molecular weight of 500 to 30,000 as determined by gel permeation chromatography, and a polydispersity index of 1.2 to 2.5. In formula (1), R represents an alkyl group having 4 to 20 carbon atoms or a phenyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m represents a number of 4 to 100, and n represents a number of 1 to 50.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyoxyalkylene compound and a surface tension regulator such as a surface modifier for electronic components comprising the polyoxyalkylene compound.

Background Art

[0002] Polyalkylene glycol derivatives can control polarity, viscosity, and reactivity by adjusting the type and degree of polymerization of the constituent alkylene oxides, thereby imparting properties such as flexibility and steric repulsion, and are used in various applications such as cosmetics, detergent compositions, water treatment agents, scale inhibitors, lubricants, plasticizers, and surface modifiers.

[0003] As surface modifiers, they are used in various industrial fields to improve the wettability, dispersibility, and coatability of hydrophilic and hydrophobic materials, such as nonionic surfactants obtained by adding alkylene oxides to aliphatic alcohols. Particularly in the field of electronic materials, they are widely used to improve the coatability of resin compositions and paints for forming printing inks, conductive pastes, color resist materials, sealants and laminated films used in displays and semiconductors.

[0004] For example, in sealants and laminated films, a resin composition containing a curable resin, a surface modifier, a solvent, etc. is coated on a substrate surface or the like. Then, it is pre-baked at about 80 to 140°C to remove the solvent, and then post-baked at about 140 to 300°C to cure the curable resin to seal the target substrate surface, or to form a cured film on the target substrate surface and then laminate a desired functional film to obtain a laminated film.

[0005] In recent years, there has been a demand for further improvement in the reliability of electronic devices. In resin compositions used in the manufacture of electronic components and electronic devices, for example, when applied to a surface protection film such as a ceramic electronic component, excellent coatability on a hydrophilic surface such as ceramics and good moisture absorption resistance after curing are required. When applied to a laminated film such as an interlayer insulating film used in displays and semiconductor applications, coatability on the hydrophilic surface of the object to be coated is required, and at the same time, a high degree of hydrophobicity is required from the viewpoint of good adhesion to the hydrophobic laminated film formed on the surface of the cured film.

[0006] Patent Document 1 shows an example of using a photosensitive resin composition capable of producing a resin film excellent in the balance between suppression of foaming during coating treatment and adhesion to a resin material constituting an electronic device by using a silicon-based surfactant or a fluorine-based surfactant as a surface protection film for electronic components.

[0007] Patent Document 2 shows a technique for hydrophobizing the surface of a substrate formed of an inorganic material such as ceramics or a resin material by performing a silylation treatment using a surface treatment agent containing a silylating agent and a solvent composed of a 5- or 6-membered lactone compound. However, such a surface treatment agent has limitations in use, such as the need to add a further hydrophobization treatment step to the film formation process, inability to be used for substrates made of materials that cannot be silylated, and the presence of solvents that are difficult to dissolve. In addition, in order to achieve both the above-mentioned coatability, moisture absorption resistance, and adhesion, it is necessary to change the hydrophilicity and hydrophobicity of the surface more significantly.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention has been made in view of such circumstances, and the problem to be solved is to provide a surface tension regulator such as a surface modifier for electronic components that has high hydrophilicity when applied to the surface of an object to be coated and can hydrophobize the surface after undergoing a manufacturing process such as heat treatment after coating.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that a predetermined polyoxyalkylene compound having a specific structure can solve the above problems. That is, the present invention relates to the following [1] and [2].

[0011] [1] A polyoxyalkylene compound represented by the following formula (1), having a number average molecular weight of 500 to 30,000 determined by gel permeation chromatography measurement and a polydispersity of 1.2 to 2.5.

[0012]

Chemical formula

[0013] (In formula (1), R represents an alkyl group having 4 to 20 carbon atoms or a phenyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m represents a number from 4 to 100, and n represents a number from 1 to 50.)

[0014] [2] A surface tension regulator comprising the polyoxyalkylene compound described in [1] above.

Effects of the Invention

[0015] According to the present invention, it is possible to provide a surface tension regulator such as a surface modifier for electronic components that has high hydrophilicity when applied to the surface of an object to be coated and can hydrophobize the surface after undergoing a manufacturing process such as heat treatment after coating.

Modes for Carrying Out the Invention

[0016] In this specification, a numerical range defined using the symbol "~" shall include the numerical values at both ends (upper limit and lower limit) of "~". For example, "2~4" represents 2 or more and 4 or less. Further, when a concentration or amount is specified, any higher concentration or amount can be associated with any lower concentration or amount. For example, when there are descriptions of "2~10 mass%" and "preferably 4~8 mass%", descriptions of "2~4 mass%", "2~8 mass%", "4~10 mass%", and "8~10 mass%" are also included.

[0017] In this specification, "(meth)acrylic" is a generic term encompassing acrylic and methacrylic.

[0018] Hereinafter, embodiments of the present invention will be described.

[0019] (Polyoxyalkylene compound) The polyoxyalkylene compound according to an embodiment of the present invention is a polyoxyalkylene compound represented by the following formula (1). The number average molecular weight determined by gel permeation chromatography measurement (hereinafter, may be referred to as GPC measurement) of this polyoxyalkylene compound is 500~30,000, and the polydispersity is 1.2~2.5. The polydispersity means the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of the polyoxyalkylene compound.

[0020] [Chemical formula]

[0021] (In formula (1), R represents an alkyl group having 4 to 20 carbon atoms or a phenyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m represents a number from 4 to 100, and n represents a number from 1 to 50.)

[0022] The polyoxyalkylene compound according to an embodiment of the present invention is a block copolymer composed of a block A represented by the following formula (2) and a block B represented by the following formula (3), as shown by the formula (1). As shown in the formula (1), both ends of the block copolymer are block B. In the formulas (2) and (3), each symbol R, n, AO, and m is the same as in the formula (1).

[0023]

Chemical formula

[0024]

Chemical formula

[0025] In the formulas (1) and (2), R may be an alkyl group having 4 to 20 carbon atoms or a phenyl group. The structure of the alkyl group is not particularly limited and may be linear or branched. From the viewpoint of improving the solubility in a solvent, it is preferable to use a branched alkyl group or a phenyl group, and more preferably to use a branched alkyl group. Examples of the alkyl group constituting R include an n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2-ethylhexyl group, and the like.

[0026] In the polyoxyalkylene compound represented by the formula (1), the block A represented by the formula (2) can be formed, for example, by addition polymerization of a glycidyl ether having an alkyl group or a phenyl group with 4 to 20 carbon atoms. This alkyl group or phenyl group becomes R in the formulas (1) and (2). Examples of such glycidyl ethers include butyl glycidyl ether, phenyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, hexadecyl glycidyl ether, octadecyl glycidyl ether, and the like. Such a predetermined glycidyl ether may be used alone or in combination of two or more. When two or more are combined, the addition form is not particularly limited and may be any of random copolymerization, block copolymerization, alternating copolymerization, and the like.

[0027] The number average molecular weight Mn of the block A represented by the formula (2) can be, for example, the value of the polymerization product obtained by addition polymerization of a predetermined glycidyl ether as described above. The molecular weight Mn of the polymer of this alkyl glycidyl ether can be selected in consideration of the number average molecular weight and polydispersity of the polyoxyalkylene compound represented by the formula (1). However, from the viewpoint of the surface tension adjusting effect, 300 to 10,000 is preferable, 300 to 5,000 is more preferable, and 500 to 2,000 is even more preferable. This molecular weight Mn can be determined by GPC measurement described later.

[0028] In the formulas (1) and (2), n means the average number of moles added of the structural units of the block A and can be calculated, for example, from the number average molecular weight Mn of the polymer of the predetermined glycidyl ether described above and the molecular weight of the structural units. n can be calculated according to the structural units of the formula (2) and the above-mentioned molecular weight Mn, and may be a number from 1 to 50, more preferably 1 to 30, even more preferably 1 to 20, and particularly preferably 1 to 10.

[0029] In formulas (1) and (3), AO may be an oxyalkylene group having 2 to 4 carbon atoms. The structure of the oxyalkylene group is not particularly limited and may be linear or branched. Also, AO may be one type or two or more types. When there are two or more types of AO, the addition form thereof may be random, block, or alternating. Examples of AO include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, etc. As AO, an oxyethylene group and oxypropylene are preferred, and an oxyethylene group is more preferred. It is preferable that the AO in block B bonded to both sides of block A is the same.

[0030] In the polyoxyalkylene compound represented by formula (1), block B represented by formula (3) can be formed, for example, by addition polymerization of an alkylene oxide having 2 to 4 carbon atoms. Examples of this alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc. Also, the alkylene oxide may be used alone or in combination of two or more.

[0031] In formulas (1) and (3), m represents the average number of moles of addition of the oxyalkylene group and may be a number from 4 to 100, preferably 4 to 50, more preferably 4 to 40, still more preferably 5 to 30, and particularly preferably 5 to 20. It is preferable that the m of AO in block B bonded to both sides of block A is the same.

[0032] The number average molecular weight Mn of the polyoxyalkylene compound represented by the formula (1) may be from 500 to 30,000, preferably from 500 to 10,000, more preferably from 500 to 5,000, and most preferably from 500 to 3,000. When the molecular weight Mn is less than 500, it is difficult to obtain a sufficient surface tension adjusting effect. When it is greater than 30,000, the melting point and viscosity of the polyoxyalkylene compound represented by the formula (1) may increase, resulting in a decrease in handleability. This molecular weight Mn uses the value determined by GPC measurement. This GPC measurement can be carried out, for example, under the conditions described later.

[0033] In the polyoxyalkylene compound represented by the formula (1), by adjusting the composition ratio of the block A represented by the formula (2), the surface tension adjusting effect of the polyoxyalkylene compound and the compatibility with the solvent and resin contained in the resin composition used during coating can be more effectively exerted. The composition ratio can be calculated based on the respective number average molecular weights Mn. For example, by synthesizing such that the ratio W of the molecular weight Mn of the block A represented by the formula (2) to the number average molecular weight Mn of the polyoxyalkylene compound represented by the formula (1) shown by the following formula is within a predetermined range, the above-mentioned functions can be more effectively exerted.

[0034] W = (number average molecular weight Mn of formula (2)) / (number average molecular weight Mn of formula (1))

[0035] From the viewpoint of obtaining a higher surface tension adjusting effect, W is preferably from 0.20 to 0.80. When it is further from 0.40 to 0.80, it is easier to balance the surface tension adjusting effect and solvent solubility. When it is from 0.40 to 0.70, a higher hydrophilic-hydrophobic change rate can be obtained.

[0036] The polydispersity (Mw / Mn) of the polyoxyalkylene compound represented by the formula (1) is from 1.2 to 2.5. Preferably it is from 1.2 to 2.0, and more preferably from 1.3 to 1.9. When the polydispersity is less than 1.2 or exceeds 2.5, sufficient hydrophobicity may not be imparted during heat treatment.

[0037] The polyoxyalkylene compound represented by formula (1), the number average molecular weight Mn, and the weight average molecular weight Mw of block A represented by formula (2) are values obtained by GPC measurement under the following conditions, and the polydispersity is a value calculated by Mw / Mn based on the obtained values. Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Column: SHODEX KF-804L (inner diameter 8 mm × length 30 cm) manufactured by Showa Denko K.K., 3 columns Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Differential refractometer (RI) Temperature: 40°C Standard: Polyethylene glycol Sample: Inject 100 μL of a THF solution with 0.1 mass% of the active ingredient

[0038] The polyoxyalkylene compound according to the embodiment of the present invention can be synthesized, for example, by the following production method.

[0039] The polyoxyalkylene compound represented by formula (1) can be produced through a process including a first step of subjecting the aforementioned predetermined glycidyl ether to addition polymerization to produce a polymer of the aforementioned predetermined glycidyl ether containing block A represented by formula (2), and a second step of subjecting the polymer obtained in the first step to an addition reaction with the aforementioned predetermined alkylene oxide.

[0040] The first step will be described. By appropriately subjecting a starting material having active hydrogen (also referred to as a starting raw material) to an addition reaction with a predetermined glycidyl ether according to the target structure, a polymer of the aforementioned predetermined glycidyl ether is obtained.

[0041] The starting material is not particularly limited, and examples include ethylene glycol, diethylene glycol, propylene glycol, glycerin monoalkyl ether, etc. However, it is preferable to use glycerin monoalkyl ether or glycerin monophenyl ether obtained by ring-opening a predetermined glycidyl ether used in the addition reaction as the starting material.

[0042] As the catalyst used in the addition reaction of the predetermined glycidyl ether, a Lewis acid catalyst or an alkali catalyst can be used. Examples of the Lewis acid catalyst include Lewis acid catalysts such as boron trifluoride and tin tetrachloride, and examples of the alkali catalyst include oxides, hydroxides, alcoholates, etc. of alkali metals and alkaline earth metals. Among these, boron trifluoride and its complexes can be preferably used from the viewpoint of easily obtaining the target molecular weight distribution. The usage amount of the catalyst is preferably 0.01 to 5.0% by mass based on the mass of the target polymer after the completion of the addition reaction.

[0043] The addition reaction of the predetermined glycidyl ether can be carried out, for example, by dropping the predetermined glycidyl ether into a reaction apparatus charged with the starting material at 0°C to 150°C in an inert gas atmosphere such as argon or nitrogen gas. The dropping rate is not particularly limited because it can be appropriately set according to the mode of the reaction apparatus. However, from the viewpoints of controlling the reaction temperature and productivity, for example, it can be set so that the dropping is completed over 1 to 10 hours. Further, in order to further progress the reaction, the reaction may be continued even after the completion of the dropping. In this case, there is no particular limitation, but for example, the reaction can be continued for about 1 to 10 hours from the end point of the dropping. The alkyl glycidyl ether can be appropriately diluted with a solvent such as toluene or methylcyclohexane and then dropped. From the viewpoint of obtaining a preferable polydispersity, the reaction temperature is preferably 20 to 130°C, more preferably 40 to 120°C. The dropping time of the glycidyl ether is preferably 1 to 7 hours, more preferably 2 to 5 hours. Furthermore, continuing the reaction for 2 to 4 hours after the completion of the dropping makes it easier to obtain a preferable polydispersity.

[0044] Here, by measuring the hydroxyl value of block A represented by formula (2), it can be confirmed that the target compound has been obtained. This hydroxyl value can adopt the value measured after subjecting the product obtained in the above-described first step to desolvation or adsorption treatment.

[0045] Next, the second step will be described. By appropriately adding an alkylene oxide to the polymer obtained in the first step according to the target structure, a predetermined polyoxyalkylene compound represented by formula (1) can be obtained. As the catalyst used for the addition reaction of the alkylene oxide, the same catalyst as in the first step can be used. Although a new catalyst may be added in the second step, from the perspective of production efficiency, the second step may be continuously carried out without removing the catalyst from the reaction solution containing the polymer obtained in the first step. The addition reaction of the alkylene oxide can be carried out, for example, by continuously adding the alkylene oxide under pressure in an inert gas atmosphere such as argon or nitrogen gas at 50 to 200 °C and 0.02 to 1.0 MPa (gauge pressure). From the perspective of obtaining a preferable polydispersity, the addition reaction of the alkylene oxide is preferably at 80 to 170 °C, more preferably at 80 to 150 °C. Also, the reaction time of the addition reaction is preferably 1 to 3 hours.

[0046] After the reaction is completed, the target polyoxyalkylene compound can be obtained by isolating the product according to a conventional method. By measuring the hydroxyl value of the product obtained here, it can be confirmed that the target compound has been obtained.

[0047] (Surface tension regulator) The surface tension regulator according to an embodiment of the present invention is composed of a predetermined polyoxyalkylene compound represented by the aforementioned formula (1). That is, the surface tension regulator may contain the polyoxyalkylene compound as an active ingredient. The polyoxyalkylene compound itself may be used as the surface tension regulator, or it may further contain additives commonly used in this technical field. Examples of the additives include thickeners, plasticizers, antistatic agents, and the like.

[0048] The surface tension regulator composed of the predetermined polyoxyalkylene compound represented by the aforementioned formula (1) can hydrophobize the surface of a molded article formed of, for example, a resin material by a method commonly practiced in this technical field. For example, it is suitable as a hydrophobizing treatment agent for resin materials such as sealants and interlayer films in electronic material applications.

[0049] Examples of applying the surface tension regulator according to an embodiment of the present invention to a resin composition for forming, for example, a sealant or an interlayer film will be described below.

[0050] This type of resin composition contains the aforementioned surface tension adjuster, resin, solvent, and other components as necessary. As the resin to which the aforementioned surface tension adjuster can be applied, any resin that is generally commonly used in this technical field may be used. Examples of such resins include poly(meth)acrylic acid-based resins, polyacetal resins, epoxy resins, polyamide resins, polyimide resins, and mixed resins thereof. As the solvent, solvents that are commonly used in this technical field can also be used. For example, organic solvents that volatilize by heating to a predetermined temperature such as toluene, xylene, acetone, methyl ethyl ketone, propylene glycol monomethyl ether acetate, etc. can be mentioned. The content of the surface tension adjuster in the resin composition can be appropriately determined according to the resin type, application, etc., but it is preferably added in an amount of 0.01 to 10 wt% based on the weight of the resin. More preferably, it is 0.05 to 7.5 wt%, still more preferably 0.1 to 5 wt%, and most preferably 1 to 5 wt%. If the addition amount is less than 0.01 wt%, a sufficient addition effect may not be obtained, and if it exceeds 10 wt%, an effect commensurate with the addition amount may not be obtained, or problems such as bleed-out may occur.

[0051] The resin composition containing the aforementioned surface tension adjuster has good hydrophilicity due to the surface tension adjuster, has good coatability when applied to a substrate with a hydrophilic surface, and after the substrate coated with the resin composition undergoes processes such as heat treatment, the surface of the coated article of the resin composition is preferably hydrophobized. The change in hydrophilicity and hydrophobicity before and after undergoing processes such as such heat treatment can be evaluated, for example, by the change in the contact angle of ion-exchanged water on the surface by the method described below.

Examples

[0052] Next, based on the examples, the embodiments of the present invention will be described in more detail.

[0053] (Synthesis Example 1: Synthesis of Polyoxyalkylene Compound 1) Into a 2 L four-necked flask, 200 g (1.0 mol) of glycerin mono-2-ethylhexyl ether as a starting material and 10 g of boron trifluoride diethyl ether as a catalyst were charged, and the temperature was raised to 45 °C under a nitrogen atmosphere while stirring. 1045 g (4.8 mol) of 2-ethylhexyl glycidyl ether charged into a dropping funnel was added dropwise to the four-necked flask over 2 hours while maintaining the reaction temperature at 45 °C ± 3 °C for reaction. Further, the reaction was continued for 2 hours at the same temperature after the dropping was completed. After the reaction was completed, dehydration treatment was carried out at 60 °C for 1 hour under reduced pressure to obtain 1180 g of a 2-ethylhexyl glycidyl ether polymer. As a result of measuring the obtained polymer by the above-mentioned GPC, the molecular weight Mn was 1000 and the hydroxyl value was 112. 560 g of the obtained 2-ethylhexyl glycidyl ether polymer was charged into a 5 L stainless steel pressure-resistant container equipped with a stirrer, a pressure gauge, a thermometer, a safety valve, a gas blowing tube, an exhaust pipe, a cooling coil, and a steam jacket, and the inside of the system was replaced with nitrogen gas. While stirring, 694 g (15.7 mol) of ethylene oxide from a separately prepared pressure-resistant container was added through a gas blowing tube while pressurizing with nitrogen gas under the conditions of 140 °C and 0.05 - 0.5 MPa (gauge pressure). After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. After cooling to 40 °C, the reaction product was taken out from the pressure-resistant container, and the catalyst was removed with an adsorbent to obtain 1350 g of polyoxyalkylene compound 1 (Compound 1). When the above-mentioned GPC measurement was carried out, the molecular weight Mn of the obtained Compound 1 was 2,200, the molecular weight Mw was 4,000, the polydispersity Mw / Mn was 1.8, and the hydroxyl value was 51.

[0054] (Synthesis Example 2: Synthesis of Polyoxyalkylene Compound 2) Polyoxyalkylene compound 2 (Compound 2) was synthesized in the same manner as in Synthesis Example 1, except that 404 g (9.2 mol) of ethylene oxide was reacted with 560 g of the 2-ethylhexyl glycidyl ether polymer obtained in the same manner as in Synthesis Example 1. When the above-mentioned GPC measurement was carried out, the molecular weight Mn of the obtained Compound 2 was 1,800, the molecular weight Mw was 3,100, the polydispersity Mw / Mn was 1.7, and the hydroxyl value was 62.

[0055] (Synthesis Example 3: Synthesis of Polyoxyalkylene Compound 3) Using 345 g (1.0 mol) of glycerin monooctadecyl ether as the starting material and 17 g of boron trifluoride diethyl etherate as the catalyst, 1290 g of an octadecyl glycidyl ether polymer was obtained in the same manner as in Synthesis Example 1, except that 1100 g (2.9 mol) of octadecyl glycidyl ether was reacted. As a result of GPC measurement of this polymer, the molecular weight Mn was 1100 and the hydroxyl value was 102. Polyoxyalkylene Compound 3 (Compound 3) was synthesized in the same manner as in Synthesis Example 1, except that 269 g (6.1 mol) of ethylene oxide was reacted with 550 g of the obtained octadecyl glycidyl ether polymer. As a result of the above-described GPC measurement, the molecular weight Mn of the obtained Compound 3 was 1,600, the molecular weight Mw was 3,000, the polydispersity Mw / Mn was 1.9, and the hydroxyl value was 70.

[0056] (Synthesis Example 4: Synthesis of Polyoxyalkylene Compound 4) Using 242 g (1.0 mol) of glycerin monododecyl ether as the starting material and 12 g of boron trifluoride diethyl etherate as the catalyst, 1,200 g of a dodecyl glycidyl ether / tetradecyl glycidyl ether copolymer was obtained in the same manner as in Synthesis Example 1, except that 1000 g (3.9 mol) of dodecyl glycidyl ether / tetradecyl glycidyl ether (mass ratio 50 / 50) was reacted. As a result of GPC measurement of this copolymer, the molecular weight Mn was 1,100 and the hydroxyl value was 102. The target polyoxyalkylene Compound 4 (Compound 4) was synthesized in the same manner as in Synthesis Example 1, except that 269 g (6.1 mol) of ethylene oxide was reacted with 550 g of the obtained dodecyl glycidyl ether / tetradecyl glycidyl ether copolymer. As a result of the above-described GPC measurement, the molecular weight Mn of the obtained Compound 4 was 1,600, the molecular weight Mw was 2,900, the polydispersity Mw / Mn was 1.8, and the hydroxyl value was 70.

[0057] (Synthesis Example 5: Synthesis of Polyoxyalkylene Compound 5) A 2-ethylhexyl glycidyl ether polymer was obtained in the same manner as in Synthesis Example 1, except that 178 g of sodium hydroxide was used instead of 10 g of boron trifluoride diethyl ether as the catalyst. As a result of GPC measurement of this polymer, the molecular weight Mn was 1,000 and the hydroxyl value was 112. Using the obtained 2-ethylhexyl glycidyl ether polymer, a polyoxyalkylene compound 5 (Compound 5) was synthesized in the same manner as in Synthesis Example 1, except that sodium hydroxide was used as the catalyst. When the above-described GPC measurement was performed, the molecular weight Mn of the obtained Compound 5 was 2,200, the molecular weight Mw was 2,400, the polydispersity Mw / Mn was 1.1, and the hydroxyl value was 51.

[0058] (Synthesis Example 6: Synthesis of polyoxyalkylene compound 7) 960 g of a phenyl glycidyl ether polymer was obtained in the same manner as in Synthesis Example 1, except that 168 g (1.0 mol) of glycerin monophenyl ether was used as the starting material and 8 g of boron trifluoride diethyl ether was used as the catalyst, and 830 g (6.1 mol) of phenyl glycidyl ether was reacted. As a result of GPC measurement of this polymer, the molecular weight Mn was 1,000 and the hydroxyl value was 112. The target polyoxyalkylene compound 7 (Compound 7) was synthesized in the same manner as in Synthesis Example 1, except that 404 g (9.2 mol) of ethylene oxide was reacted with 560 g of the obtained phenyl glycidyl ether polymer. When the above-described GPC measurement was performed, the molecular weight Mn of the obtained Compound 7 was 1,800, the molecular weight Mw was 3,100, the polydispersity Mw / Mn was 1.7, and the hydroxyl value was 62.

[0059] (Synthesis Example 7: Synthesis of polyoxyalkylene compound 8) A polyoxyalkylene compound 8 (Compound 8) was synthesized in the same manner as in Synthesis Example 1, except that 740 g (12.7 mol) of propylene oxide was reacted with 560 g of the 2-ethylhexyl glycidyl ether polymer obtained in the same manner as in Synthesis Example 1. When the above-described GPC measurement was performed, the molecular weight Mn of the obtained Compound 8 was 2,200, the molecular weight Mw was 4,000, the polydispersity Mw / Mn was 1.8, and the hydroxyl value was 51.

[0060] (Synthesis Example 8: Synthesis of Polyoxyalkylene Compound 9) A 2-ethylhexyl glycidyl ether polymer was obtained in the same manner as in Synthesis Example 1, except that a 3 L four-necked flask was used and 2414 g (13.0 mol) of 2-ethylhexyl glycidyl ether was used. As a result of GPC measurement of this polymer, the molecular weight Mn was 2,000 and the hydroxyl value was 56. Polyoxyalkylene Compound 9 (Compound 9) was synthesized in the same manner as in Synthesis Example 1, except that 805 g (18.3 mol) of ethylene oxide was reacted with 560 g of the obtained 2-ethylhexyl glycidyl ether polymer. When the above-mentioned GPC measurement was carried out, the molecular weight Mn of the obtained Compound 2 was 4,400, the molecular weight Mw was 8,400, the polydispersity Mw / Mn was 1.9, and the hydroxyl value was 13.

[0061] Table 1 shows the correspondence of Polyoxyalkylene Compounds 1 to 5 and 7 to 9 obtained in Synthesis Examples 1 to 8 with Formula (1) and the results of GPC measurement. In addition, Compound 6 used as a surface tension regulator in Comparative Example 2 described later is also shown.

[0062]

Table 1

[0063] (Evaluation) (Evaluation of Solubility of Compounds 1 to 9 in Solvents) Compounds 1 to 9 used as surface tension regulators in Examples 1 to 8 and Comparative Examples 1 and 2 described later were dissolved at room temperature to 1 wt% in 20 milliliters of transparent glass containers of toluene and propylene glycol monomethyl ether acetate, respectively. The appearance during dissolution was visually confirmed, and insoluble / stratified was marked as ×, dispersed as ○, and completely dissolved / transparent as ◎. The results are shown in Table 2.

[0064] (Evaluation of Change Rate of Contact Angle by Resin Composition) (Example 1) 1 g of an acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd., Orinox KC-7000F), 20 g of toluene, and 0.05 g of Compound 1 (5 wt% based on the acrylic resin) as a surface tension modifier were mixed, and a resin composition was prepared according to a conventional method. The obtained resin composition was spin-coated on the surface of a glass substrate and dried at 80 °C under a reduced pressure of 4 kPa for 2 h (pre-baking) to prepare a test piece with a coating film of the resin composition formed on the surface of the glass substrate. Ion-exchanged water was dropped onto the surface of the coating film of this test piece, and Contact Angle 1 was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name DropMaster DM-301). After measuring Contact Angle 1, the test piece was further heated at 180 °C for 2 h (post-baking) to prepare a test piece with a coated product (cured film) of the resin composition formed on the surface of the glass substrate. Ion-exchanged water was dropped onto the surface of the cured film of this test piece, and Contact Angle 2 was measured with the above contact angle meter. The change rates of the measured Contact Angles 1 and 2 were calculated by the following formula, and the changes in the hydrophilic and hydrophobic properties of the surface of the test piece before and after post-baking were evaluated. The evaluation criteria were: × when the change rate was less than 3.0, ○ when it was 3.0 or more and less than 6.0, and ◎ when it was 6.0 or more. Change rate of contact angle [%] = Contact Angle 2 / Contact Angle 1 × 100

[0065] <<Examples 2 to 8, Comparative Examples 1 to 3>> A resin composition was prepared in the same manner as in Example 1 except that the surface tension modifier and its addition amount were as shown in Table 2, and the change rate of the contact angle was calculated to evaluate the changes in the hydrophilic and hydrophobic properties of the surface of the test piece before and after post-baking. The results are shown in Table 2.

[0066]

Table 2

[0067] Examples 1 to 8 using the predetermined polyoxyalkylene compounds 1 to 4 and 7 to 9 represented by formula (1) show that a coating film with a lower contact angle 1 and higher hydrophilicity can be formed compared to Comparative Example 3 without addition. Also, it can be seen that the contact angle 2 is higher compared to Comparative Example 3, the hydrophobicity is improved after post-baking, and the surface tension adjusting effect is excellent. Moreover, since the solubility in an organic solvent is good, it can be used together with various solvents suitable for the type of resin and baking conditions.

[0068] On the other hand, in Comparative Example 1 where Compound 5 was added, since the degree of dispersion of Compound 5 deviated from the predetermined range, it was found that the surface tension adjusting effect could not be obtained. Also, in Comparative Example 2 using Compound 6, since it is an ethylene oxide adduct of stearyl alcohol with a structure different from the polyoxyalkylene compound represented by formula (1), the surface tension adjusting effect was not obtained. In Comparative Example 3, since no surface tension adjuster was added, there was no change in the contact angle, and the surface characteristics of the acrylic resin were shown.

Industrial Applicability

[0069] A resin composition containing a predetermined polyoxyalkylene compound represented by formula (1) as a surface tension adjuster has high hydrophilicity during coating of the resin composition and can hydrophobize the surface after undergoing a manufacturing process such as heat treatment. The polyoxyalkylene compound is suitable as a surface tension adjuster such as a surface modifier for electronic parts used for hydrophobizing the surface of inorganic materials such as ceramics and the surface of molded articles of resin materials.

Claims

1. A polyoxyalkylene compound represented by the following formula (1), having a number average molecular weight of 500 to 30,000 and a polydispersity of 1.2 to 2.5, as determined by gel permeation chromatography measurement. 【Chemical 1】 (In formula (1), R represents an alkyl group or a phenyl group having 4 to 20 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m represents a number from 4 to 100, and n represents a number from 1 to 50.)

2. A surface tension regulator comprising the polyoxyalkylene compound according to Claim 1.

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