JP6469377B2 - Polyglycerin-based resin plasticizer, ceramic slurry composition containing the same, and ceramic molded body - Google Patents

Description

  The present invention relates to a polyglycerin-based resin plasticizer composed of a specific (poly) glycerin fatty acid ester, a ceramic slurry composition containing the same, and a ceramic molded body.

  A ceramic green sheet, which is one of ceramic molded bodies, is used when manufacturing ceramic circuit boards, multilayer ceramic capacitors, etc., and is a slurry composition in which ceramic powder, binder resin, plasticizer, and organic solvent are mixed. The product is formed into a sheet shape. In recent years, with the increase in functionality and miniaturization of electronic devices, multilayer electronic components such as multilayer ceramic capacitors have increased in capacity and size, and in response, ceramic green sheets are required to be thinner. ing. However, by thinning the ceramic green sheet, there is a problem that the sheet strength is lowered and the occurrence rate of sheet defects is increased.

  Therefore, in order to improve the strength of the ceramic green sheet, measures such as using a binder resin having a high degree of polymerization have been taken, but with this, there is a concern that the flexibility of the ceramic green sheet is lowered. For this reason, flexibility is imparted by adding a plasticizer.

  As a plasticizer for the ceramic green sheet, a phthalic acid plasticizer such as dioctyl phthalate is disclosed (Patent Document 1). However, the safety of phthalic acid plasticizers has been pointed out due to problems such as environmental hormones, and their use is limited. Patent Document 2 describes an example in which a glycol plasticizer such as triethylene glycol di-2-ethylhexanoate is used as a plasticizer. However, since these plasticizers have low polarity, the compatibility with the binder resin is low, and the formed ceramic green sheet has insufficient flexibility.

  On the other hand, polyvinyl butyral resin, which is one of polyvinyl acetal resins, is mainly used for the binder resin of the ceramic green sheet. As a plasticizer of polyvinyl butyral resin, in addition to the above plasticizer, polyglycerol 2-ethylhexanoic acid partial ester and glycerol fatty acid ester are disclosed (Patent Documents 3 and 4). However, both of these are disclosures within a range composed only of a polyvinyl butyral resin and a plasticizer, and there is no disclosure in a ceramic green sheet system containing ceramic powder.

Japanese Patent No. 5462700 Japanese Patent No. 4870919 JP 2013-249462 A Special table 2011-503258 gazette

  In view of such circumstances, an object of the present invention is to provide a plasticizer having good compatibility with a polyvinyl acetal resin and to provide a ceramic green sheet excellent in flexibility.

  As a result of intensive studies by the present inventors, it is composed of (poly) glycerin having an average degree of polymerization of 1 to 2 calculated from the hydroxyl value, straight chain and branched fatty acids having 2 to 10 carbon atoms ( It has been found that the above problems can be solved by using a poly) glycerin fatty acid ester. Furthermore, in the above (poly) glycerin fatty acid ester, when the esterification rate calculated from the hydroxyl value is in the range of 20 to 80 mol%, it is possible to provide a ceramic slurry composition having a more excellent function, and a ceramic green sheet. I found.

  By blending the (poly) glycerin fatty acid ester of the present invention into a ceramic slurry composition comprising a polyvinyl acetal resin, a ceramic powder, an organic solvent, and other additives, the flexibility of the ceramic green sheet can be improved.

  Hereinafter, the present invention will be described based on an embodiment. However, the scope of the present invention is not limited to this embodiment, and a mode in which changes are made without departing from the spirit of the present invention also belongs to the present invention. . However, parts and% are based on weight unless otherwise specified.

  The polyglycerin-based resin plasticizer in the present invention is a (poly) glycerin fatty acid ester obtained by esterifying a (poly) glycerin having an average degree of polymerization of 1 to 2 calculated from a hydroxyl value with a fatty acid. This (poly) glycerin fatty acid ester may be used alone or in combination of two or more.

(Poly) glycerin fatty acid ester (poly) glycerin used in the present invention has an average degree of polymerization of 1 to 2 calculated from the hydroxyl value. In the present specification, the average degree of polymerization (n) of (poly) glycerin calculated from the hydroxyl value is a value calculated by terminal analysis, and is calculated from the following formulas (formula 1) and (formula 2). The
(Formula 1) Molecular weight = 74n + 18
(Formula 2) Hydroxyl value = 56110 (n + 2) / Molecular weight The hydroxyl value is a numerical value indicating the size of the number of hydroxyl groups contained in (poly) glycerin, and is a free hydroxyl group contained in 1 g of (poly) glycerin. Refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid required to acetylate. The number of milligrams of potassium hydroxide is calculated according to the Japan Oil Chemists 'Society edited by “The Japan Oil Chemists' Society, Standard Oil Analysis Test Method (I), 2003 edition”.

  The constituent fatty acid of the (poly) glycerin fatty acid ester used in the present invention is a saturated or unsaturated fatty acid having 2 to 10 carbon atoms, and the structure thereof may be linear or branched. Examples include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, and the like. These fatty acids may be used alone or in combination of two or more.

The solubility parameter (SP value) of the (poly) glycerin fatty acid ester of the present invention is in the range of 9.5 to 14.5. In the present specification, the solubility parameter can be calculated by the method (Fedors method) described in “Polymer Engineering and Science, Vol. 14, No. 2, p. 147-154 (1974)”. The SP value is represented by the following formula (Formula 3).
(Expression 3) SP value (δ) = (ΔH / V) 1/2
However, (DELTA) H in Formula 3 represents molar heat of vaporization (cal), and V represents molar volume (cm < ³ >). Further, as ΔH and V, the sum of molar evaporation heat (ΔH) and the sum of molar volumes (V) of atomic groups described in pages 151 to 153 of the above-mentioned document can be used. Those with close SP values are easy to mix with each other (high compatibility), and those with SP values far apart are indexes indicating that they are difficult to mix. In (poly) glycerin fatty acid ester, when SP value is 9.5 or more and 14.5 or less, since compatibility with resin is excellent, it is preferred.

The esterification rate of the (poly) glycerin fatty acid ester of the present invention is preferably 20 to 80 mol%. Within this range, the compatibility with the polyvinyl acetal resin tends to be good, and the flexibility of the ceramic green sheet is improved. Here, the esterification rate is the average degree of polymerization of polyglycerol (n) calculated from the hydroxyl value by end group analysis, the number of hydroxyl groups (n + 2) of this (poly) glycerin, added to (poly) glycerin. It is a value calculated by the number of moles of fatty acid (M), and is calculated from the following formula (Formula 4).
(Formula 4) (M / (n + 2)) × 100 = esterification rate (%)

  The (poly) glycerin fatty acid ester of the present invention is synthesized by a general esterification reaction. As an example, the reaction is allowed to proceed while heating to a reaction temperature of 160 ° C. or higher under synthesis conditions equipped with a reflux apparatus and removing the produced water out of the system.

  The (poly) glycerin fatty acid ester of the present invention can be synthesized without a catalyst or in the presence of a catalyst. Examples of catalysts that can be used include basic catalysts and acidic catalysts. As the basic catalyst, sodium hydroxide, potassium hydroxide and the like are preferable. Further, as the acidic catalyst, any of acidic phosphoric acid esters such as (ortho) phosphoric acid, polyphosphoric acid, 2-ethylhexyl acid phosphate, oleyl acid phosphate, stearyl acid phosphate is preferable, and these are used alone. Alternatively, two or more types may be used in combination. In addition, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, stannous chloride, stannic chloride, dibutyltin bis (2-ethylhexanoate), dibutyltin diacetate, tetraethoxytitanium, tetraisopropoxytitanium, etc. Although it is mentioned, it is not limited to these.

  The present invention provides the aforementioned (poly) glycerin fatty acid ester and also provides a polyvinyl acetal resin composition containing the same. The content ratio of the (poly) glycerin fatty acid ester blended as a plasticizer is preferably 3 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. When the content ratio of the (poly) glycerin fatty acid ester is less than 3 parts by weight, the plasticizing effect is not sufficiently exhibited, the flexibility of the polyvinyl acetal resin composition is lowered, and when it exceeds 100 parts by weight, the polyvinyl acetal resin This range is preferable because it causes a decrease in mechanical properties.

  The polyvinyl acetal resin used for the polyvinyl acetal resin composition of the present invention is not particularly limited, and examples thereof include a polyvinyl formal resin, a polyvinyl butyral resin, and a polyvinyl acetoacetal resin. Among these, polyvinyl butyral resin is preferable.

  The polyvinyl butyral resin is not particularly limited, but preferably has an average polymerization degree of 200 to 5000, and preferably has a butyralization degree of 50 mol% or more from the viewpoint of compatibility with a plasticizer.

  The ceramic slurry composition of the present invention contains an organic solvent, ceramic powder and the like in addition to the plasticizer and the polyvinyl acetal resin.

  The organic solvent is not particularly limited. For example, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol and isopropanol, aromatic hydrocarbons such as toluene and xylene, methyl propionate, ethyl propionate and butanoic acid. Examples thereof include esters such as methyl, ethyl butanoate, methyl pentanoate and ethyl pentanoate, glycols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, α-terpineol and butyl cellosolve acetate, or terpenes. These organic solvents may be used alone or in combination of two or more.

  The ceramic powder is not particularly limited. For example, alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, boron nitride, aluminum nitride, ferrite, steer Examples thereof include tight, magnesia, sialon, forsterite. These ceramic powders may be used alone or in combination of two or more.

  The ceramic slurry composition of the present invention may contain a polyvinyl alcohol resin, an acrylic resin, a cellulose resin, and a urethane resin in addition to the polyvinyl acetal resin as a binder resin.

  In addition to the above (poly) glycerin fatty acid ester, the ceramic slurry composition of the present invention includes a phthalate ester plasticizer such as dibutyl phthalate and di-2-ethylhexyl phthalate, diisononyl adipate, dioctyl adipate, Aliphatic dibasic acid ester plasticizers such as dioctyl sebacate, trimetic acid ester plasticizers such as tri-2-ethylhexyl trimet, glycol ester plasticizers such as triethylene glycol di-2-ethylhexanoate, etc. A general plasticizer may be contained.

  Moreover, the ceramic slurry composition of the present invention may contain conventionally known additives such as a lubricant, a dispersant, an antistatic agent, and an antioxidant as long as the effects of the present invention are not impaired.

  There is no restriction | limiting in particular as a method of manufacturing the ceramic slurry composition of this invention, A conventionally well-known method can be used. For example, a method of mixing the plasticizer, a binder resin containing a polyvinyl acetal resin, a ceramic powder, an organic solvent, and various additives to be added as necessary using various mixers such as a ball mill, three rolls, etc. It is done.

  There is no restriction | limiting in particular as a ceramic molded object obtained using the ceramic slurry composition of this invention, The shaping | molding produced by conventionally well-known shaping | molding methods, such as a tape molding method, an extrusion molding method, a casting molding method, and a gel casting molding method The body is mentioned.

  There is no restriction | limiting in particular as a manufacturing method of the ceramic green sheet obtained using the ceramic slurry composition of this invention, It can manufacture using a conventionally well-known method. Examples thereof include a method in which a ceramic slurry composition is cast on a peelable support such as a polyethylene terephthalate film (PET), the solvent is distilled off by heating or the like, and then peeled off from the support.

  EXAMPLES Hereinafter, although this invention is shown concretely based on an Example, this invention is not limited to these Examples. The (poly) glycerin used this time is glycerin (purified glycerin, manufactured by Sakamoto Pharmaceutical Co., Ltd.) and diglycerin (diglycerin S, manufactured by Sakamoto Pharmaceutical Co., Ltd., average polymerization degree 2).

(Synthesis of (poly) glycerin fatty acid ester)
187.2 g of glycerin and 586.0 g of caprylic acid were put in a reaction vessel and esterified at 180 ° C. to 220 ° C. under a nitrogen stream to obtain a glycerin fatty acid ester (PGFE1) having an SP value of 10.2. Similarly, PGFE 2 to 13 were synthesized by changing the type of (poly) glycerin, the type of fatty acid, and the molar ratio of fatty acid to (poly) glycerin. The synthesized (poly) glycerin fatty acid ester is shown in Table 1.

Example 1
5 parts by weight of glycerin fatty acid ester (PGFE1) and 10 parts by weight of polyvinyl butyral resin (average polymerization degree 800, butyralization degree 75 to 80 mol%) in 85 parts by weight of a mixed solvent of toluene: ethanol = 50: 50 (v / v) In addition, it was dissolved by stirring. 100 parts by weight of barium titanate (BT-01, manufactured by Sakai Chemical Industry Co., Ltd.) as a ceramic powder was added to the obtained resin solution and mixed uniformly to obtain a ceramic slurry composition. The obtained ceramic slurry composition was applied onto a PET film, the solvent was dried, and then peeled from the PET film to obtain a ceramic green sheet.

(Examples 2 to 12)
A ceramic slurry composition was prepared in the same manner as in Example 1 except that (poly) glycerin fatty acid ester (PGFE2 to 12) was used instead of glycerin fatty acid ester (PGFE1) used in Example 1, A ceramic green sheet was prepared.

(Example 13)
Instead of 5 parts by weight of glycerin fatty acid ester (PGFE1) used in Example 1, 2.5 parts by weight of glycerin fatty acid ester (PGFE1) and 2.5 parts by weight of polyglycerin fatty acid ester (PGFE2) were used. A ceramic slurry composition was prepared in the same manner as in Example 1 to produce a ceramic green sheet.

(Example 14)
Implementation was performed except that 2.5 parts by weight of glycerin fatty acid ester (PGFE1) and 2.5 parts by weight of glycerin fatty acid ester (PGFE4) were used instead of 5 parts by weight of glycerin fatty acid ester (PGFE1) used in Example 1. A ceramic slurry composition was prepared in the same manner as in Example 1 to produce a ceramic green sheet.

(Example 15)
2.5 parts by weight of glycerin fatty acid ester (PGFE1) and 10 parts by weight of polyvinyl butyral resin (average polymerization degree 800, butyralization degree 75 to 80 mol%) 85% by weight of a mixed solvent of toluene: ethanol = 50: 50 (v / v) And dissolved with stirring. 100 parts by weight of barium titanate (BT-01, manufactured by Sakai Chemical Industry Co., Ltd.) as a ceramic powder was added to the obtained resin solution and mixed uniformly to obtain a ceramic slurry composition. The obtained ceramic slurry composition was applied onto a PET film, the solvent was dried, and then peeled from the PET film to obtain a ceramic green sheet.

(Example 16)
10 parts by weight of glycerin fatty acid ester (PGFE1) and 10 parts by weight of polyvinyl butyral resin (average polymerization degree 800, butyralization degree 75 to 80 mol%) in 85 parts by weight of a mixed solvent of toluene: ethanol = 50: 50 (v / v) In addition, it was dissolved by stirring. 100 parts by weight of barium titanate (BT-01, manufactured by Sakai Chemical Industry Co., Ltd.) as a ceramic powder was added to the obtained resin solution and mixed uniformly to obtain a ceramic slurry composition. The obtained ceramic slurry composition was applied onto a PET film, the solvent was dried, and then peeled from the PET film to obtain a ceramic green sheet.

(Example 17)
A polyvinyl butyral resin (average polymerization degree 800, butyralization degree 70 to 75 mol%) was used in place of the polyvinyl butyral resin (average polymerization degree 800 and butyralization degree 75 to 80 mol%) used in Example 1. A ceramic slurry composition was prepared in the same manner as in Example 1 to produce a ceramic green sheet.

(Example 18)
A polyvinyl butyral resin (average polymerization degree 800, butyralization degree 80 to 85 mol%) was used in place of the polyvinyl butyral resin (average polymerization degree 800, butyralization degree 75 to 80 mol%) used in Example 1. A ceramic slurry composition was prepared in the same manner as in Example 1 to produce a ceramic green sheet.

(Example 19)
A polyvinyl butyral resin (average polymerization degree 1600, butyralization degree 75 to 80 mol%) was used in place of the polyvinyl butyral resin (average polymerization degree 800 and butyralization degree 75 to 80 mol%) used in Example 1. A ceramic slurry composition was prepared in the same manner as in Example 1 to produce a ceramic green sheet.

(Comparative Examples 1-2)
A ceramic slurry composition in the same manner as in Example 1 except that glycerin fatty acid ester (PGFE12) or polyglycerin fatty acid ester (PGFE12) was used instead of glycerin fatty acid ester (PGFE1) used in Example 1. And a ceramic green sheet was prepared.

(Comparative Example 3)
A ceramic slurry composition was prepared in the same manner as in Example 1 except that triethylene glycol di-2-ethylhexanoate was used instead of the polyglycerol fatty acid ester (PGFE1) used in Example 1. A ceramic green sheet was prepared.

  The ceramic green sheets obtained in Examples 1 to 19 and Comparative Examples 1 to 3 were evaluated for flexibility as shown below. Moreover, the compatibility of the plasticizer used for each Example and the comparative example and polyvinyl butyral resin was evaluated by the method shown below. The evaluation results are shown in Table 2.

(Flexibility)
About the obtained ceramic green sheet, the autograph (AG-IS, Shimadzu Corporation make) was used, the tension test was implemented according to JIS-7217, and distortion (%) was calculated | required.

(Compatibility)
A mixture of polyvinyl butyral resin / plasticizer = 1/100 (weight ratio) was allowed to stand at 160 ° C. for 1 hour, and then the appearance when cooled to room temperature was visually determined. The transparent and uniform appearance of the solution was marked with ◎, the slightly turbid one with ◯, the white turbid with Δ, and the precipitate with x.

  From the result of Table 2, the (poly) glycerin fatty acid ester comprised from the (poly) glycerin whose average degree of polymerization calculated from a hydroxyl value is 1-2 and a C2-C10 fatty acid was used as a plasticizer. In this case, the strain is 10% or more, and the flexibility of the ceramic green sheet is higher than when glycerin fatty acid ester, polyglycerin fatty acid ester, and triethylene glycol di-2-ethylhexanoate outside the above range are used. Was good. Similarly, the compatibility with the polyvinyl acetal resin was also good. Among these, when the SP value of the (poly) glycerin fatty acid ester is in the range of 9.5 to 14.5 and the esterification rate calculated from the hydroxyl value is in the range of 20 to 80 mol%, a more excellent effect is shown.

Claims (2)

A ceramic molded body obtained using a ceramic slurry composition containing a resin plasticizer, a polyvinyl acetal resin, a ceramic powder, and an organic solvent,
The resin plasticizer is a (poly) glycerin fatty acid ester composed of (poly) glycerin having an average degree of polymerization of 1 to 2 calculated from a hydroxyl value and a linear or branched fatty acid having 2 to 10 carbon atoms. A ceramic molded body characterized by the above. A ceramic green sheet obtained using the ceramic slurry composition according to claim 1.