Polyoxyalkylene polyglyceryl ether methacrylate compound, active energy ray-curable resin composition containing same, and cured product thereof

Abstract

In applications of a coating agent such as a hard coat layer, a lining agent, an adhesive agent, an adhesive agent, a coating material, an ink, a resist material for an optical material, an electronic material, a printed circuit board, and the like, not only adhesion but also water resistance, solvent resistance, and alkali resistance are required for an active energy ray-curable resin composition and a cured product thereof. Therefore, provided are: a compound which forms a cured product having excellent water resistance, solvent resistance, and alkali resistance without impairing adhesion; and an active energy ray-curable resin composition. The problem is solved by a polyoxyalkylene polyglyceryl ether methacrylate compound having a structure represented by formula 1. [Chemical Formula 1]

Description

Technical Field

[0001] This invention relates to an active energy ray-curable resin composition and its cured product capable of forming a water-resistant cured film without compromising light transmittance or adhesion. Background Technology

[0002] For active energy ray-curable resin compositions, rapid curing and high productivity make them widely used as coating agents, lining agents, adhesives, bonding agents, coatings, inks, and photoresist materials for optical materials, electronic materials, and printed circuit boards.

[0003] Resin compositions cured by active energy radiation are widely used as environmentally friendly materials due to their rapid curing, high productivity, and solvent-free application. They are applied in coatings, linings, adhesives, bonding agents, paints, inks, optical materials, electronic materials, medical resins, laminates, printed circuit boards, photoresists, and semiconductor sealants. For these materials, a good fit with the substrate and sufficient hardness of the cured product are sometimes required. While the hardness can be improved using the following active energy radiation-cured compositions, sufficient fit is not achieved. These compositions utilize polyfunctional (meth)acrylates containing three or more (meth)acryloyl groups per molecule.

[0004] To date, inventors have invented polyfunctional acrylate compounds with a polyglycerol backbone and active energy ray-curable resin compositions and cured products containing such polyfunctional acrylate compounds (Patent Document 1) in an effort to solve the problem of adhesion.

[0005] However, in applications such as coatings, linings, adhesives, bonding agents, paints, inks, and resists for optical materials, electronic materials, and printed circuit boards, active energy ray-curable resin compositions and their cured products are required not only to have good adhesion, but also to be water-resistant, solvent-resistant, and alkali-resistant.

[0006] Existing technical documents Patent documents Patent document 1: Japanese Patent Application Publication No. 2018-178071. Summary of the Invention

[0007] The problem that the invention aims to solve Therefore, the object of the present invention is to provide compounds and active energy ray-cured resin compositions that form cured products with excellent water resistance, solvent resistance and alkali resistance without compromising adhesion.

[0008] Solution for solving the problem The present invention includes the following inventions and discoveries that can solve the above-mentioned problems.

[0009] (1) A polyoxyethylene polyglycerol ether methacrylate compound having the structure shown in Formula 1, [Chemistry 1] (In the formula, R represents a hydrogen atom or a methacryloyl group. Not all of them are hydrogen atoms. In addition, AO represents ethylene oxide with 2 carbon atoms and / or propylene oxide with 3 carbon atoms. k, l, and m are the addition numbers of the olefinic oxygen, which are 0 to 15 respectively. Not all of k, l, and m are 0. n represents the average degree of polymerization of polyglycerol calculated from the hydroxyl value, which is 2 to 10.)

[0010] (2) The polyoxyethylene polyglycerol ether methacrylate compound according to (1) has a weight-average molecular weight of 500 to 1500.

[0011] (3) The polyalkylene polyglycerol ether methacrylate compound according to (1) or (2), wherein the AO comprises at least propylene oxide having 3 carbon atoms.

[0012] (4) An active energy ray-curable resin composition containing the polyoxyethylene polyglycerol ether methacrylate compound described in (1).

[0013] (5) A cured product obtained by curing the active energy ray-curable resin composition described in (4).

[0014] (6) A laminate, characterized in that it has a layer comprising the cured material described in (5) on a substrate.

[0015] (7) An electronic component comprising the laminate described in (6).

[0016] The effects of the invention The active energy radiation-curable resin composition containing the polyalkylene polyglycerol ether methacrylate compound of the present invention and its cured product exhibit excellent water resistance, solvent resistance and alkali resistance without compromising adhesion, and are suitable for use on substrates such as plastic materials, as well as inorganic substrates such as metals and glass. Detailed Implementation

[0017] The present invention will now be described based on embodiments. However, the scope of the present invention is not limited to the embodiments described below, and includes modifications made without prejudice to the spirit of the invention. It should be noted that the "~" indicating the scope includes both an upper and lower limit.

[0018] The average degree of polymerization (n) of the polyglycerol backbone constituting the polyalkylene polyglycerol ether methacrylate compound of the present invention is 2 to 10, preferably 2 to 6, and more preferably 2 to 4. The average degree of polymerization (n) mentioned herein can be calculated from the hydroxyl value. Generally, the hydroxyl value is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to hydroxyl groups when 1 gram of sample is acetylated. For polyglycerol, it refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 gram of (poly)glycerol, indicating the number of hydroxyl groups. Polyglycerol with an average degree of polymerization of 2 is represented by diglycerol, polyglycerol with an average degree of polymerization of 3 is represented by triglycerol, and polyglycerol with an average degree of polymerization of 4 is represented by tetraglycerol. Commercially available products include diglycerol S, R-PG, PGL-S, polyglycerol #310, polyglycerol #500, and polyglycerol #750 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.). If the average degree of polymerization is greater than 10, it affects the manufacturing productivity and is therefore not preferred. Furthermore, if the average degree of polymerization increases, the viscosity also increases, which also leads to a deterioration in operability.

[0019] The polyalkylene polyglycerol ether methacrylate compound of the present invention undergoes an addition of AO (hereinafter referred to as AO) to the polyglycerol backbone. Examples of olefins used include ethylene oxide with two carbon atoms and / or propylene oxide with three carbon atoms. From the viewpoint of improving water resistance, it is preferable that the olefin contains at least propylene oxide with three carbon atoms. When using two olefins that add to the hydroxyl groups of the polyglycerol backbone, random addition / block addition can be selected, but there are no particular limitations. k, l, and m represent the number of olefin additions, which range from 0 to 15. Preferably, the number of additions ranges from 0 to 8. Not all of k, l, and m are 0. When the number of additions is greater than 15, it is difficult to simultaneously achieve good adhesion and water resistance for the polyalkylene polyglycerol ether methacrylate compound, the active energy radiation-curable resin composition containing the compound, and the cured product thereof. Furthermore, the manufacture of the polyalkylene polyglycerol ether methacrylate compound suffers from problems such as increased purification difficulties in the manufacturing process, which is not preferred.

[0020] There are no particular limitations on the method for manufacturing the polyalkylene polyglycerol ether methacrylate compound of the present invention. For example, examples include: an addition reaction of alkylene oxide with polyglycerol to obtain polyoxyalkylene polyglycerol ether; a dehydration esterification method in which methacrylic acid reacts with the hydroxyl groups of the above-mentioned polyoxyalkylene polyglycerol ether and extracts the generated water out of the system, thereby obtaining an esterified product; and an transesterification method in which a methacrylate of a lower alcohol reacts with a terminal hydroxyl group and extracts the generated lower alcohol out of the system, thereby obtaining an esterified product.

[0021] From the viewpoint of the functionality of the cured product, the preferred reaction ratio for methacrylates is a polyalkylene polyglycerol ether methacrylate compound obtained by reacting an average of 3 or more hydroxyl groups relative to the number of hydroxyl groups in the polyoxyethylene polyglycerol ether.

[0022] The polyalkylene polyglycerol ether methacrylate compound of the present invention preferably has a weight-average molecular weight of 500 to 1500. Cured polyalkylene polyglycerol ether methacrylate compounds with a weight-average molecular weight of 500 to 1500 exhibit superior light transmittance, adhesion, and water resistance.

[0023] When preparing a polyalkylene polyglycerol ether methacrylate compound of Formula 1 by reacting methacrylic acid with the hydroxyl groups of polyoxyalkylene polyglycerol ether, a free radical polymerization inhibitor may also be used after the reaction or purification. The polyoxyalkylene polyglycerol ether is obtained by adding olefinic oxygen to polyglycerol.

[0024] Examples of free radical polymerization inhibitors include quinone-based inhibitors such as p-methoxyphenol, hydroquinone, methoxyhydroquinone, and p-tert-butylcatechol; alkylphenol-based inhibitors such as 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol; and amine-based inhibitors such as alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine.

[0025] The active energy ray-curable resin composition of the present invention can be cured by known methods. Active energy rays are a general term for electromagnetic waves such as electron beams, X-rays, ultraviolet rays, and visible light in the low wavelength region; ultraviolet rays are preferred due to the simplicity and widespread availability of commonly used devices. Many types of devices capable of irradiating ultraviolet light can be used, and any choice can be made. The light source can be a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED, etc.

[0026] When using ultraviolet light as the active energy ray for curing, a free radical polymerization photoinitiator is required. Any known photoinitiator can be used. Examples include intramolecular cleavage initiators such as benzyl ketals, α-hydroxyacetophenones, aminoacetophenones, acylphosphine oxides, oxime esters, and benzoin; and hydrogen abstraction initiators such as benzophenones, thioxanones, and aryl biimidazoles. These can be used alone or in combination of two or more.

[0027] When a photopolymerization initiator is required, its usage is preferably 0.1 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the polyoxyethylene polyglycerol ether methacrylate compound.

[0028] In addition, when using photopolymerization initiators, one photosensitizer or a combination of two or more photosensitizers can be used.

[0029] In the active energy ray-curable resin composition containing the polyalkylene polyglycerol ether methacrylate compound of the present invention, free radical polymerizable compounds such as (meth)acrylate monomers and polyurethane (meth)acrylate monomers may be used in addition to the methacrylate compound used in the present invention, without impairing the effects of the present invention. They may be used alone or in combination of two or more.

[0030] The active energy radiation-curable resin composition containing the polyalkylene polyglycerol ether methacrylate compound of the present invention may, as needed, be blended with non-reactive polymer resins such as polyester elastomers, polyurethane elastomers, and acrylic polymers, as well as reactive polymer resins such as diallyl phthalate, diallyl isophthalate, polyurethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, and acrylic polymers, without impairing the effects of the present invention.

[0031] The polymeric resin is preferably 0 to 1000 parts by weight, and more preferably 0 to 300 parts by weight, relative to 100 parts by weight of the polyoxyethylene polyglycerol ether methacrylate compound.

[0032] In addition, when using polymer resins in active energy ray compositions, one type of polymer resin or a combination of two or more polymer resins may be used.

[0033] The active energy radiation-curable resin composition containing the polyalkylene polyglycerol ether methacrylate compound of the present invention may be appropriately mixed with organic solvents such as acetone, methyl ethyl ketone, ethanol, toluene, hexane, ethyl acetate, methyl cellosolve, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate, without impairing the effects of the present invention.

[0034] The organic solvent is preferably 0 to 2000 parts by weight, more preferably 0 to 1000 parts by weight, relative to 100 parts by weight of the polyoxyethylene polyglycerol ether methacrylate compound.

[0035] In addition, when using organic solvents in active energy ray compositions, one organic solvent or a combination of two or more organic solvents may be used.

[0036] The active energy radiation-curable resin composition containing the polyalkylene polyglycerol ether methacrylate compound of the present invention may, within the scope not impairing the effect of the present invention, be appropriately blended with surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, as well as additives such as leveling agents, defoamers, silane coupling agents, antioxidants, ultraviolet absorbers, colorants, light stabilizers, heat stabilizers, polymerization inhibitors, pigments, metal oxide microparticle dispersions, and antifogging agents.

[0037] The polyalkylene polyglycerol ether methacrylate compound of the present invention and the active energy radiation-curable resin composition containing the compound can form a cured film with excellent water resistance without compromising permeability and adhesion. When cured using active energy radiation, various forms such as coatings, films, and three-dimensional shapes can be produced using known methods. Furthermore, it is applicable to a wide range of substrates, including plastic substrates such as polyethylene terephthalate resin (PET resin), polycarbonate resin (PC), polystyrene resin (PS), and polyolefin resins (PP resin, PE resin), and polymethyl methacrylate (PMMA), as well as inorganic substrates such as metals and glass.

[0038] In addition, its cured products can be widely used in coatings, linings, adhesives, bonding agents, paints, inks, and resists for optical materials, electronic materials, printed circuit boards, etc. Example

[0039] The following examples and embodiments are provided to illustrate the present invention, but the present invention is not limited by these examples.

[0040] <Synthesis example 1> In a reaction vessel, a 9-molar adduct of diglycerol in propylene oxide (manufactured by Sakamoto Pharmaceutical Co., Ltd.), toluene, p-toluenesulfonic acid, hydroquinone monomethyl ether, and methacrylic acid are added, and a dehydration esterification reaction is carried out to obtain methacrylate (M1) of the 9-molar adduct of diglycerol in propylene oxide.

[0041] <Synthesis example 2> By using the same method as in Synthesis Example 1, methacrylic acid was reacted with a compound obtained by adding 12 moles of propylene oxide to triglycerides (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give methacrylate (M2), a 12 moles adduct of triglycerides to propylene oxide.

[0042] <Synthesis example 3> By using the same method as in Synthesis Example 1, methacrylic acid was reacted with a compound obtained by adding 18 moles of propylene oxide to tetraglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give methacrylate (M3), which is an 18 moles adduct of propylene oxide to tetraglycerol.

[0043] <Synthesis example 4> By using the same method as in Synthesis Example 1, methacrylic acid was reacted with a compound obtained by adding 8 moles of propylene oxide and 16 moles of ethylene oxide to triglycerides (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give methacrylate (M4), which is an adduct of 8 moles of propylene oxide and 16 moles of ethylene oxide to triglycerides.

[0044] <Synthesis example 5> By using the same method as in Synthesis Example 1, methacrylic acid was reacted with a compound obtained by adding 12 moles of ethylene oxide to triglycerides (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give methacrylate (M5), a 12 moles adduct of triglycerides to ethylene oxide.

[0045] <Synthesis example 6> By using the same method as in Synthesis Example 1, methacrylic acid was reacted with a compound obtained by adding 6 moles of ethylene oxide to tetraglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give methacrylate (M6), a 6 moles adduct of tetraglycerol to ethylene oxide.

[0046] <Synthesis Example 7> By using the same method as in Synthesis Example 1, methacrylic acid was reacted with a compound obtained by adding 25 moles of propylene oxide and 25 moles of ethylene oxide to diglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give methacrylic acid ester (M7) of the diglycerol adduct of propylene oxide and ethylene oxide.

[0047] <Synthesis example 8> By using the same method as in Synthesis Example 1, acrylic acid was reacted with a compound obtained by adding 40 moles of ethylene oxide to diglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give an acrylate of the 40 moles ethylene oxide adduct of diglycerol (A1).

[0048] <Synthesis Example 9> By using the same method as in Synthesis Example 1, acrylic acid was reacted with a compound obtained by adding 12 moles of ethylene oxide to tetraglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give acrylate of the 12 moles ethylene oxide adduct of tetraglycerol (A2).

[0049] <Synthesis example 10> By using the same method as in Synthesis Example 1, acrylic acid was reacted with a compound obtained by adding 60 moles of ethylene oxide to tetraglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give acrylate (A3) of the 60 moles ethylene oxide adduct of tetraglycerol. <Synthesis Example 11> By using the same method as in Synthesis Example 1, acrylic acid was reacted with a compound obtained by adding 18 moles of propylene oxide to tetraglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give acrylate of the 18 moles propylene oxide adduct of tetraglycerol (A4).

[0050] <Synthesis Example 12> By using the same method as in Synthesis Example 1, acrylic acid was reacted with a compound obtained by adding 60 moles of propylene oxide to tetraglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) to give an acrylate of the 60 moles propylene oxide adduct of tetraglycerol (A5).

[0051] <Properties of Polyoxyethylene Polyglycerol Ether (Meth)acrylate Compounds> 1. Determination of weight-average molecular weight The weight-average molecular weight of polyoxyethylene polyglycerol ether (meth)acrylate compounds was evaluated by gel permeation chromatography (GPC). GPC-based analyses were performed under the conditions described below, and the weight-average molecular weights obtained were used for evaluation.

[0052] • Analytical instruments and analytical conditions Liquid delivery unit: LC-20AD (manufactured by Shimadzu Corporation) Column oven: CTO-20A (manufactured by Shimadzu Corporation) Differential refractive index detector: RID-10A (manufactured by Shimadzu Corporation) Pillar: TOSHO Protective Pillar HXL-L + TOS HO TSKgel G2000HXL + TOSHO TSK gel G2500HXL (manufactured by TOSHO) Column temperature: 40℃ Mobile phase: Tetrahydrofuran Liquid delivery speed: 1.0mL / min Standard sample: PEG calibration kit 2. Viscosity determination For the viscosity of polyoxyethylene polyglycerol ether (meth)acrylate compounds, an E-type viscometer (HBDV-II+Pro CP, manufactured by BROOKFIELD) was used. A CPE-40 spindle was used, with a collection volume of 0.5 mL, and the viscosity was measured at 25°C.

[0053] Evaluation of coatings using polyoxyethylene polyglycerol ether (meth)acrylate compounds Preparation of cured coating Five parts of 1-hydroxycyclohexylphenyl ketone (Irgacure 184: BASF Japan) were uniformly mixed with 100 parts of polyoxyethylene polyglycerol ether (meth) acrylate compound as a photopolymerization initiator to obtain an active energy radiation-curable resin composition. This composition was then coated onto a polyethylene terephthalate film (Lumira 100-S10, Toray Industries, Inc., 100 μm thick) using a rod coater. A cured coating was obtained using a conveyor belt UV irradiation device equipped with a high-pressure mercury lamp (product name: Igrantai ECS-401GX, Igranficus Inc.).

[0054] <Evaluation of Transparency> The transparency of the coating film is assessed by visual inspection.

[0055] 〇: The coating film is transparent and smooth.

[0056] ×: The coating film is discolored or cloudy, or the coating film has unevenness.

[0057] <Evaluation of water resistance> 1. Evaluation of water contact angle The water contact angle was determined using a DM-702 interfacial tensiometer (Kyowa Interfacial Chemicals), employing the θ / 2 method to measure the contact angle between the coating film and the water droplet. Ten measurements were taken for each sample, and the average value was recorded as the water contact angle. The obtained water contact angles were evaluated as follows.

[0058] ○: Water contact angle is 65° or higher △: Water contact angle is greater than 50° and less than 65° ×: Water contact angle less than 50° 2. Immersion test After immersing the coating film in a water bath at 80°C for 3 hours, observe the peeling of the coating film and evaluate it as follows.

[0059] ○: No peeling of coating or film at all ×: Peeling of coating or film. <Evaluation of solvent resistance> For solvent resistance, add 1 drop of methanol to the coating film, rinse the solvent off the coating film with deionized water after 1 minute, and then visually observe the surface of the coating film as follows for evaluation.

[0060] 〇: Peeling of the coating or film without coating ×: Peeling of coating or film. <Evaluation of Fit> The adhesion of the coating film was evaluated according to the checkerboard tape method specified in JIS K 5600-5-6. The evaluation was conducted according to the specified checkerboard tape method. A 100-square checkerboard pattern was made on the coating film using a cutter and a cutting guide. Transparent tape was applied to the checkerboard pattern, and the number of squares that remained intact upon removal was confirmed using an optical microscope (BZ-8100, KEYENCE). The results were evaluated as follows.

[0061] 〇: The peeling of the coating film is 0 grids. △: Coating peeling is less than 10 squares. ×: The coating has peeled off more than 10 squares.

[0062] In the table, compounds M1 to M7 and A1 to A5 used the polyoxyethylene polyglycerol ether (meth) acrylate compounds described in Synthesis Examples 1 to 12.

[0063] The polyoxyethylene polyglycerol ether methacrylate compound of this embodiment has a lower viscosity and superior workability compared to polyoxyethylene polyglycerol ether acrylate. Furthermore, due to its low reactivity, the coating solution or resist solution containing it also exhibits excellent storage stability. Moreover, the cured coating film obtained by curing the polyoxyethylene polyglycerol ether methacrylate compound of this embodiment not only has excellent water resistance but also excellent adhesion to the substrate, making it suitable for use as a coating material or resist material.

[0064] The compound of this embodiment has a polyglycerol backbone. Polyether methacrylate compounds having a polyglycerol backbone or resin compositions containing such compounds can be polymerized to form a three-dimensional mesh structure, thus becoming a matrix resin for various plastic materials. Furthermore, due to the high hydrophobicity of the compound of this embodiment, it can be easily compounded with various resins.

Claims

1. A polyoxyethylene polyglycerol ether methacrylate compound having the structure shown in Formula 1, [Chemistry 1] In the formula, R represents a hydrogen atom or a methacryloyl group, where, Not all are hydrogen atoms; in addition, AO represents ethylene oxide with 2 carbon atoms and / or propylene oxide with 3 carbon atoms; k, l, and m are the addition numbers of olefinic oxygen, ranging from 0 to 15, where k, l, and m are not all 0; n represents the average degree of polymerization of polyglycerol calculated from the hydroxyl value, ranging from 2 to 10.

2. The polyoxyethylene polyglycerol ether methacrylate compound according to claim 1, wherein the weight-average molecular weight is 500 to 1500.

3. The polyalkylene polyglycerol ether methacrylate compound according to claim 2, wherein, The AO contains at least propylene oxide with 3 carbon atoms.

4. An active energy ray-curable resin composition, wherein, It contains the polyoxyethylene polyglycerol ether methacrylate compound as described in claim 1.

5. A cured product obtained by curing the active energy ray-curable resin composition of claim 4.

6. A laminated body, characterized in that, The substrate has a layer comprising the cured material as described in claim 5.

7. An electronic component comprising the laminate of claim 6.

8. A polyoxyethylene polyglycerol ether methacrylate compound, which is the polyalkylene polyglycerol ether methacrylate compound according to claim 3, characterized in that, It is a methacrylate of a 9-molar adduct of diglycerol to propylene oxide.

9. A polyoxyethylene polyglycerol ether methacrylate compound, which is the polyalkylene polyglycerol ether methacrylate compound according to claim 3, characterized in that, It is a methacrylate of the 12-molar adduct of triglycerides and propylene oxide.

10. A polyoxyethylene polyglycerol ether methacrylate compound, which is the polyalkylene polyglycerol ether methacrylate compound according to claim 3, characterized in that, It is a methacrylate of the 18-molar adduct of tetraglycerol to propylene oxide.

11. A polyoxyethylene polyglycerol ether methacrylate compound, which is the polyalkylene polyglycerol ether methacrylate compound according to claim 3, characterized in that, It is a methacrylate of the adduct of triglycerides in 8 moles of propylene oxide and 16 moles of ethylene oxide.

12. A polyoxyethylene polyglycerol ether methacrylate compound, which is the polyalkylene polyglycerol ether methacrylate compound according to claim 3, characterized in that, It is a methacrylate of a 12-molar adduct of triglycerides and ethylene oxide.

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